Combined seals, compositions, and methods of making the same

ABSTRACT

A combined sealing member is provided that includes a composition comprising two or more polyolefin elastomers selected from the group consisting of a dense, a micro-dense and a dynamic silane-crosslinked polyolefin elastomer having a respective density of less than 0.90 g/cm 3 , less than 0.70 g/cm 3 , and less than 0.60 g/cm 3 . The combined sealing member exhibits a compression set of from about 5.0% to about 35.0%, as measured according to ASTM D 395 (22 hrs @ 70° C.).

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority under 35 U.S.C. § 119(e) to U.S.Provisional Patent Application No. 62/497,954 filed Dec. 10, 2016,entitled “WEATHERSTRIP, COMPOSITION INCLUDING SILANE-GRAFTED POLYOLEFIN,AND PROCESS OF MAKING A WEATHERSTRIP,” which is herein incorporated byreference in its entirety.

FIELD OF THE DISCLOSURE

The disclosure generally relates to compositions that may be used toform seals, and more particularly, to compositions used to form sealswith combinations of silane-crosslinked polyolefin elastomers invehicles and methods for manufacturing these compositions and seals.

BACKGROUND OF THE DISCLOSURE

The motor vehicle industry is continuously manufacturing and developingsealing elements and sections having low friction and abrasionresistance properties. These elements and sections can be extruded fromcertain polymeric materials. One example of an extrudedabrasion-resistant section is a static seal. Static seals, such asweatherstrips, are mounted on an automobile window to provide a sealbetween the glass and the automobile body to prevent wind noise, waterleaks, and particulate matter from entering the automobile. Anotherexample of an extruded abrasion-resistant seal is a dynamic seal.Dynamic seals, such as weatherstrips, are typically employed to sealparts that are capable of motion relative to one another. According tofurther examples of these seals, foaming agents can be employed togenerate porosity in the seals to offer further weight savings.

Weatherstrip formulations that make contact with various sections ofautomotive glass doors, and/or other sections of an automotive bodytraditionally utilize thermoplastic vulcanizates (TPV),styrene-ethylene/butylene-styrene copolymer (SEBS), or ethylenepropylene diene monomer (EPDM) rubber to achieve desired sealingperformance. Monolithic TPV, SEBS and EPDM materials typically exhibitdensities in the range of 0.75 g/cm³ to 1.3 g/cm³, depending on whetherfoaming agents are employed. While monolithic TPV-, SEBS- and EPDM-basedseals offer certain property and density ranges that can suitable forparticular sealing applications, various portions of the seals mayrequire differing properties and/or densities relative to other portionsof the same seal. Further, TPVs are relatively easy to process, butsealing performance can be limited in terms of resilience or sealingability over time and material costs tend to be high. Similarly, EPDMrubber formulations often require many ingredients (e.g., carbon black,petroleum-based oil, zinc oxide, miscellaneous fillers such as calciumcarbonate or talc, processing aids, curatives, blowing agents, and manyother materials to meet performance requirements), which tend toincrease their material cost.

EPDM-based seals are also costly from a process stand point. The EPDMconstituent ingredients are typically mixed together in a one- ortwo-step process prior to shipping to an extrusion facility. At theextrusion facility, the ingredients and rubber compound(s) are extrudedtogether to form a final material, which is subsequently formed intoautomotive glass contacting weatherstrips. Hence, the extrusion processused to manufacture weatherstrips can include many stages, depending onthe type of EPDM or other types of resins, and may additionally requirelong lengths of curing ovens. For example, extrusion lines of up to 80yards in length that are powered by natural gas and/or electricity maybe required. Much of the natural gas and/or electricity is used to fuelhot air ovens, microwaves, infrared ovens, or other types of equipmentused to vulcanize the EPDM rubber compounds. The vulcanization processalso produces fumes that must be vented and monitored to comply withenvironmental requirements. Overall, the processes used to fabricatethese traditional EPDM-based seals can be very time consuming, costly,and environmentally unfriendly.

Mindful of the drawbacks associated with current TPV-, SEBS- andEPDM-based sealing technologies, the automotive industry has a need forthe development of new compositions and methods for manufacturing seals,such as weatherstrips, that are simpler, lighter in weight, lower incost, have superior long-term load loss (LLS) (i.e., ability to seal theglass and window for a long term), offer variable properties within agiven part, and are more environmentally friendly.

SUMMARY OF THE DISCLOSURE

According to one aspect of the present disclosure, a combined sealingmember is provided that includes a composition comprising two or morepolyolefin elastomers selected from the group consisting of a dense, amicro-dense and a dynamic silane-crosslinked polyolefin elastomer havinga respective density of less than 0.90 g/cm³, less than 0.70 g/cm³, andless than 0.60 g/cm³. The combined sealing member exhibits a compressionset of from about 5.0% to about 35.0%, as measured according to ASTM D395 (22 hrs @ 70° C.).

According to another aspect of the present disclosure, a combinedsealing member is provided that includes a composition comprising afirst and a second polyolefin elastomer. The first elastomer comprises amicrodense silane-crosslinked polyolefin elastomer having a density ofless than 0.70 g/cm³. Further, the second elastomer comprises a densesilane-crosslinked polyolefin elastomer having a density of less than0.90 g/cm³ or a dynamic silane-crosslinked polyolefin elastomer having adensity of less than 0.60 g/cm³. In addition, the combined sealingmember exhibits a compression set of from about 5.0% to about 35.0%, asmeasured according to ASTM D 395 (22 hrs @ 70° C.).

According to a further aspect of the present disclosure, a combinedsealing member is provided that includes a composition comprising afirst and a second polyolefin elastomer. The first elastomer comprises adense silane-crosslinked polyolefin elastomer having a density of lessthan 0.90 g/cm³. Further, the second elastomer comprises a dynamicsilane-crosslinked polyolefin elastomer having a density of less than0.60 g/cm³. In addition, the combined sealing member exhibits acompression set of from about 5.0% to about 35.0%, as measured accordingto ASTM D 395 (22 hrs @ 70° C.).

These and other aspects, objects, and features of the present disclosurewill be understood and appreciated by those skilled in the art uponstudying the following specification, claims, and appended drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings:

FIG. 1 is a front perspective view of a vehicle having a plurality ofweatherstrip static seals according to some aspects of the presentdisclosure;

FIG. 2 is a side perspective view of a front door portion of the vehiclepresented in FIG0.1;

FIG. 3 is a cross-sectional view of a below-belt weatherstrip sealaccording to some aspects of the present disclosure;

FIG. 4 is a cross-sectional view of a primary weatherstrip sealaccording to some aspects of the present disclosure;

FIG. 5 is a schematic perspective view of a plurality of combined sealsused in the vehicle presented in FIG. 1 according to aspects of thedisclosure;

FIGS. 6A-6F are a variety of cross-sectional views of the representativecombined seals provided in FIG. 5 according to some aspects of thepresent disclosure;

FIG. 6G is a schematic cross-sectional view of a combined sealaccompanied with cross-sectional and enlarged views of an actualcombined seal for illustration, according to aspects of the disclosure;

FIG. 7 is a schematic reaction pathway used to produce asilane-crosslinked polyolefin elastomer according to some aspects of thepresent disclosure;

FIG. 8 is a flow diagram of a method for making a static seal with asilane-crosslinked polyolefin elastomer using a two-step Sioplasapproach according to some aspects of the present disclosure;

FIG. 9A is a schematic cross-sectional view of a reactive twin-screwextruder according to some aspects of the present disclosure;

FIG. 9B is a schematic cross-sectional view of a single-screw extruderaccording to some aspects of the present disclosure;

FIG. 10 is a flow diagram of a method for making a combined seal with asilane-crosslinked polyolefin elastomer using a one-step Monosilapproach according to some aspects of the present disclosure;

FIG. 11 is a schematic cross-sectional view of a reactive single-screwextruder according to some aspects of the present disclosure;

FIG. 12 is a graph illustrating the stress/strain behavior of a densesilane-crosslinked polyolefin elastomer compared to EPDM compounds;

FIG. 13 is a graph illustrating the lip compression set of inventivedense silane-crosslinked polyolefin elastomers and comparativepolyolefin elastomers;

FIG. 14 is a graph illustrating the lip set recovery of inventive densesilane-crosslinked polyolefin elastomers and comparative polyolefinelastomers;

FIG. 15 is a graph illustrating the relaxation rate of several densesilane-crosslinked polyolefin elastomers and comparative polyolefinelastomers;

FIG. 16 is a graph illustrating the stress/strain behavior of aninventive dense silane-crosslinked polyolefin elastomer;

FIG. 17 is a graph illustrating the compression set of EPDM, TPV, and adense silane-crosslinked polyolefin elastomer as plotted with respect tovarious test temperatures and time conditions;

FIG. 18 is a graph illustrating the compression set of EPDM, TPV, and adense silane-crosslinked polyolefin elastomer as plotted with respect totemperatures ranging from 23° C. to 175° C.;

FIG. 19 is a graph illustrating the compression set of TPV and severaldense silane-crosslinked polyolefin elastomers as plotted with respectto 23° C. and 125° C. temperatures;

FIG. 20 is a graph illustrating the load versus position behavior of adynamic silane-crosslinked polyolefin elastomer, as compared to loadversus position behavior of comparative EPDM compounds; and

FIG. 21 is a set of micrographs of dynamic silane-crosslinkedelastomers, as processed with a supercritical gas-injected fluid or achemical foaming agent, according to aspects of the disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

For purposes of description herein the terms “upper,” “lower,” “right,”“left,” “rear,” “front,” “vertical,” “horizontal,” and derivativesthereof shall relate to the combined seals of the disclosure as orientedin the vehicle shown in FIG. 1. However, it is to be understood that thedevice may assume various alternative orientations and step sequences,except where expressly specified to the contrary. It is also to beunderstood that the specific devices and processes illustrated in theattached drawings, and described in the following specification aresimply exemplary embodiments of the inventive concepts defined in theappended claims. Hence, specific dimensions and other physicalcharacteristics relating to the embodiments disclosed herein are not tobe considered as limiting, unless the claims expressly state otherwise.

All ranges disclosed herein are inclusive of the recited endpoint andindependently combinable (for example, the range of “from 2 to 10” isinclusive of the endpoints, 2 and 10, and all the intermediate values).The endpoints of the ranges and any values disclosed herein are notlimited to the precise range or value; they are sufficiently impreciseto include values approximating these ranges and/or values.

A value modified by a term or terms, such as “about” and“substantially,” may not be limited to the precise value specified. Theapproximating language may correspond to the precision of an instrumentfor measuring the value. The modifier “about” should also be consideredas disclosing the range defined by the absolute values of the twoendpoints. For example, the expression “from about 2 to about 4” alsodiscloses the range “from 2 to 4.”

As used herein, the term “and/or,” when used in a list of two or moreitems, means that any one of the listed items can be employed by itself,or any combination of two or more of the listed items can be employed.For example, if a composition is described as containing components A,B, and/or C, the composition can contain A alone; B alone; C alone; Aand B in combination; A and C in combination; B and C in combination; orA, B, and C in combination.

Referring to FIGS. 1-6G, various combined sealing members are provided.In general, the combined sealing members of the disclosure include acomposition having two or more dense, micro-dense and dynamicsilane-crosslinked polyolefin elastomers, each with a density less than0.90 g/cm³, less than 0.70 g/cm³, and less than 0.60 g/cm³,respectively. The combined sealing member can exhibit a compression setof from about 5.0% to about 35.0% measured according to ASTM D 395 (22hrs @ 70° C.). The silane-crosslinked polyolefin elastomer can be adense elastomer produced from a blend including a first polyolefinhaving a density less than 0.86 g/cm³, a second polyolefin having acrystallinity less than 40%, a silane crosslinker, a grafting initiator,and a condensation catalyst. The polyolefin elastomer can also be adynamic or sponge blend including a first polyolefin having a densityless than 0.86 g/cm³, a second polyolefin having a crystallinity lessthan 60%, a silane crosslinker, a grafting initiator, a condensationcatalyst, and a foaming agent. The polyolefin elastomer can also be amicrodense blend including a first polyolefin having a density less than0.86 g/cm³, a second polyolefin having a crystallinity less than 60%, asilane crosslinker, a grafting initiator, a condensation catalyst, and amicroencapsulated foaming agent.

Referring to FIG. 1, vehicle 10 is provided having a variety of combinedsealing members 12 (e.g., weatherstrip seals). The vehicle 10 is shownas a sports utility vehicle (SUV) but the type of vehicle 10 is notmeant to be limiting and can include, for example, a car, minivan,truck, commercial vehicle, or any other wheeled motorized vehicle. Thevehicle 10 and the combined sealing members 12 described herein are forillustrative purposes only and are not to be construed as limiting toonly vehicles 10, for example, the combined sealing members 12 couldadditionally be used in the building construction industry, thetransportation industry, the electronics industry, the footwearindustry, and the roofing industry.

Referring now to FIG. 2, a portion of the vehicle 10 (see FIG. 1)including a front door 14 is provided. The door 14 includes a windowopening 18 and a window 22 that can be selectively raised and loweredrelative to the window opening 18. The combined sealing member 12 in theform of a window weatherstrip seal 26 surrounds perimeter portions ofthe window 22 (e.g., side and upper portions when the window is closed).The window weatherstrip seal 26 may be used to seal portions of the door14 against the surface and/or edges of the glass window 22. The windowweatherstrip seal 26 may be formed using separate weatherstrip portionsincluding a beltline weatherstrip seal 12, 34, and a below-beltweatherstrip seal 12, 74 (see also FIG. 3) positioned in first andsecond belt portions 38, 42 that engage different perimeter portions ofthe window 22. The first and second belt portions 38, 42 can be locatedin an interior cavity of the door 14 and the below-belt weatherstripseal 74 can be positioned within the first and second belt portions 38,42. In some aspects, the beltline and below-belt weatherstrip seals 34,74 can be integrally joined together as a module or the combined windowweatherstrip seal 26. An inner edge of the window opening 18, as definedby the door 14, may be referred to as a beltline 30. Extending along thebeltline 30 is the beltline weatherstrip seal 34 that joins the window22 to the surrounding door 14 and makes up a portion of the windowweatherstrip seal 26.

The terms “weatherstrip” and “weatherstrip seal”, as used herein, areexamples of a seal. The term “seal”, as used herein, means a device orsubstance that is used to join two surfaces together. The surfaces usedherein may include the various types of surfaces found on, for example,automobiles, structures, windows, roofs, electronic devices, footwear,and/or any other industry or product where seals can be used to helpminimize and/or eliminate the transmission of noise, water, orparticulate matter through the respective surfaces.

The seals used for the various combined sealing members 12 (e.g.,weatherstrip seals 26) disclosed herein are fabricated or manufacturedfrom two or more different silane-crosslinked polyolefin elastomers. Insome aspects, the different silane-crosslinked polyolefin elastomers caneach make up one or more different strips, gripping portions, bodies,pins, and/or surfaces of the combined seal. As noted earlier, staticseals generally have little or no relative motion between the matingsurfaces being sealed. In some aspects, the combined seals of thedisclosure include one or more portions made from a densesilane-crosslinked polyolefin elastomer. As used herein, a “dense”silane-crosslinked polyolefin elastomer has a density of less than 0.90g/cm³. The synthesis and processing methods used to produce this densesilane-crosslinked polyolefin elastomer and its specialized materialproperties are disclosed herein.

In aspects of the disclosure, the combined seals include one or moreportions made from a micro-dense silane-crosslinked polyolefinelastomer, as typically used in micro-dense seals. Micro-dense seals aregenerally used where there is little to moderate motion between themating surfaces being sealed. As used herein, a “micro-dense” or“microdense” silane-crosslinked polyolefin elastomer includes amicroencapsulated foaming agent and has a density less than 0.70 g/cm³or, more specifically, a density from about 0.60 g/cm³to about 0.69g/cm³.

In aspects of the disclosure, the combined seals include one or moreportions made from a sponge silane-crosslinked polyolefin elastomer, astypically used in dynamic seals. Dynamic seals are generally used whenthere is motion between the mating surfaces. As used herein, a “dynamic”or “sponge” silane-crosslinked polyolefin elastomer includes a chemicaland/or physical foaming agent and has a density less than 0.60 g/cm³ or,more specifically, a density from about 0.50 g/cm³to about 0.59 g/cm³.

Referring now to FIG. 3, a cross-sectional view of the windowweatherstrip seal 26, which is exemplary of the combined sealing members12 of the disclosure (see FIGS. 1, 2), in the form of the below-beltweatherstrip seal 74 (see also FIG. 2) is provided. In some aspects, thebelow-belt weatherstrip seal 74 may have an outer rigid support member78 provided as a generally U-shaped component that receives or supportsthe below-belt weatherstrip seal 74. The member 78 can includeupstanding first and second legs 82, 86 that form a channel base 90which can receive the below-belt weatherstrip seal 74. The below-beltweatherstrip seal 74 may be unsupported, i.e., in this configuration thebelow-belt weatherstrip seal 74 does not have a rigid support memberencased within the rubber or EPDM extrusion of which it is made. Firstand second legs 94, 98 of the below-belt weatherstrip seal 74 extendgenerally upwardly and outwardly from a base portion 102, giving thebelow-belt weatherstrip seal 74 a generally U-shaped conformationadapted to receive a perimeter edge of the window 22. First and secondretaining flanges 106, 110 are provided along outer edges of the baseportion 102 while first and second flexible seal lips 114, 118 areflexibly joined at outer ends of the respective first and second legs94, 98. The first and second flexible seal lips 114, 118 and the firstand second retaining flanges 106, 110 may be formed of differentpolyolefin compounds (e.g., dense, dynamic and/or micro-dense polyolefinblends) than the remaining rubber of the below-belt weatherstrip seal 74employed in the legs 94, 98. Further, those portions of the below-beltweatherstrip seal 74 including the first and second legs 94, 98 and baseportion 102 can be adapted to engage the window 22 using a hardenedsurface (e.g., metal oxides and carbon allotropes), while the first andsecond seal lips 114, 118 may have a low friction surface (e.g.,graphite powder and polytetrafluoroethylene) to engage the window 22surface.

Referring now to FIG. 4, a cross-sectional representation of a combinedsealing member 12 in the form of a primary weatherstrip seal 120 isprovided. In particular, the primary weatherstrip seal 120 includes acombination of three types of silane-crosslinked polyolefin elastomersaccording to the disclosure: a main body member 124 comprising amicro-dense silane-crosslinked polyolefin elastomer, a bulb member 128comprising a sponge silane-crosslinked polyolefin elastomer, and aretainer pin 132 comprising a dense silane-crosslinked polyolefinelastomer. The main body member 124 can be secured to the door panel 62or other portion of the door 14 (see FIG. 2) of the vehicle 10 by anyconventional or known means for doing so, including but not limited to,for example, the retainer pin 132, though this is not a limiting featureof the disclosure. As such, any means known in the relevant art forsecuring the primary weatherstrip seal 120 to a surface of the vehicle10 may be used. The bulb member 128 can provide a seal between the door14 and other portions of the vehicle 10, for example, when the primaryweatherstrip seal 120 is brought into contact and compressed between thetwo respective surfaces. As will be appreciated by one skilled in theart, the body of the vehicle 10 and the inner portion of the door 14represented in FIG. 4 may be substituted by any two adjoining surfacesthat would benefit from the presence of one or more primary weatherstripseals 120 impervious to environmental conditions. As such, the body ofthe vehicle 10 and the inner portion of the door 14 are merelyrepresentative of adjoining surfaces and are not considered to belimiting features of the disclosure. Other locations where primaryweatherstrip seals 120 could be applied include, for example, doorpanels, body seals, trunk lid seals, door-to-door seals, rocker seals,and hood seals (e.g., as provided in FIG. 5).

Referring to FIG. 5 and FIGS. 6A-6H, an isolated exploded schematic viewof a plurality of combined sealing members 12 in the form of variousweatherstrip seals (e.g., seals 122, 126, 130, 146, 150 and 154) thatcan be used in the vehicle 10 (see FIG. 1) is provided. The combinedsealing members 12 may be configured as various weatherstrip seals,including those coupled to the perimeter of the door, such as asecondary door seal 122 (see FIG. 6A) and a primary door seal 126 (seeFIG. 6B). The dynamic sealing member 12 may also be in the form of arocker seal 130 (see FIG. 6C) used to seal an underbody with a foot wellof the vehicle 10 (see FIG. 1). Further, a liftgate seal 146 (see FIG.6D) may be configured to provide a functional seal used to couple a backhatch with a flip glass seal 150 (see FIG. 6E) positioned against aliftable rear glass window. Similarly, pillar margin seal 154 (see FIG.6F) may be configured to seal another pillar of the vehicle 10.

Referring now to FIGS. 6A-6F, a variety of cross-sectional views of thecombined sealing members 12 depicted in FIG. 5 are provided thatinclude: the secondary door seal 122, the primary door seal 126, therocker seal 130, the liftgate seal 146, the flip glass seal 150 and thepillar margin seal 154. The structures of each of the combined sealingmembers 12 may be varied based on the particular application, e.g.,sealing a glass surface to a portion of the vehicle 10 (see FIG. 1).More particularly, the various combined sealing members 12, as shown inFIGS. 6A-6F, can include combinations of bodies, legs, lips, flanges,sections, gripping portions, and edges (as previously described inconnection with FIG. 5), and further comprise two or more types ofsilane-crosslinked polyolefin elastomers (e.g., sponge (or dynamic),dense and micro-dense silane-crosslinked polyolefin elastomers). In someaspects, the combined sealing member 12 may be extruded around a pieceof metal to provide greater structural stability as shown in outer beltdynamic seal 122, and first center pillar dynamic seal 146. In someaspects, the combined sealing member 12 may have a flock materialcoupled to a surface of the member 12. The term “flock”, as used herein,is defined to mean a light powder, comprised of ground wood or cottonfiber, used as a coating, extender, and/or filler with the dynamic,dense and/or micro-dense silane-crosslinked polyolefin elastomers of themember 12 to provide a surface having a lower surface energy and/orlower friction surface.

Referring now to FIG. 6G, a schematic cross-sectional view of amicrodense sealing member 136 (i.e., as exemplary of the combinedsealing members 12 shown in FIGS. 1 and 2) is provided, and accompaniedwith cross-sectional micrographs of an actual combined sealing member.As is evident from the micrograph, the microdense sealing member 136includes a microdense seal portion 34 that comprises a microdensesilane-crosslinked polyolefin elastomer and a dense seal portion 38 thatcomprises a dense silane-crosslinked polyolefin elastomer. Notably, theenlarged micrograph demonstrates that the microdense seal portion 34includes porosity 42 that can be developed through the incorporation offoaming agents in the elastomer during processing, as discussed ingreater detail below. As also outlined below, and as evident in FIG. 3,the pore size of the microdense portion can be adjusted or varied by thechoice of foaming agent and/or processing conditions.

Thus, the disclosure focuses on the composition, method of making thecomposition, and the corresponding material properties for three typesof silane-crosslinked polyolefin elastomers (dynamic, dense andmicro-dense) used to make combined seals, e.g., combined sealing members12. The combined sealing member 12 is formed from a silane-graftedpolyolefin where the silane-grafted polyolefin may have a catalyst addedto form a silane-crosslinkable polyolefin elastomer. Thissilane-crosslinkable polyolefin may then be crosslinked upon exposure tomoisture and/or heat to form the final silane-crosslinked polyolefinelastomers or blend. In aspects, the dense silane-crosslinked polyolefinelastomer or blend includes a first polyolefin having a density lessthan 0.90 g/cm³, a second polyolefin having a crystallinity of less than40%, a silane crosslinker, a graft initiator, and a condensationcatalyst. As such, the silane-crosslinked polyolefin elastomer or blendcan include a dense elastomer produced from a blend including a firstpolyolefin having a density less than 0.86 g/cm³, a second polyolefinhaving a crystallinity less than 40%, a silane crosslinker, a graftinginitiator, and a condensation catalyst. The polyolefin elastomer canalso be a dynamic or sponge blend including a first polyolefin having adensity less than 0.86 g/cm³, a second polyolefin having a crystallinityless than 60%, a silane crosslinker, a grafting initiator, acondensation catalyst, and a foaming agent. The polyolefin elastomer canalso be a micro-dense blend including a first polyolefin having adensity less than 0.86 g/cm³, a second polyolefin having a crystallinityless than 60%, a silane crosslinker, a grafting initiator, acondensation catalyst, and a microencapsulated foaming agent.

First Polyolefin

The first polyolefin can be a polyolefin elastomer including an olefinblock copolymer, an ethylene/α-olefin copolymer, a propylene/α-olefincopolymer, EPDM, EPM, or a mixture of two or more of any of thesematerials. Exemplary block copolymers include those sold under the tradenames INFUSE™, an olefin block co-polymer (the Dow Chemical Company) andSEPTON™ V-SERIES, a styrene-ethylene-butylene-styrene block copolymer(Kuraray Co., LTD.). Exemplary ethylene/α-olefin copolymers includethose sold under the trade names TAFMER™ (e.g., TAFMER DF710) (MitsuiChemicals, Inc.), and ENGAGE™ (e.g., ENGAGE 8150) (the Dow ChemicalCompany). Exemplary propylene/α-olefin copolymers include those soldunder the trade name VISTAMAXX 6102 grades (Exxon Mobil ChemicalCompany), TAFMER™ XM (Mitsui Chemical Company), and Versify (DowChemical Company). The EPDM may have a diene content of from about 0.5to about 10 wt %. The EPM may have an ethylene content of 45 wt % to 75wt %.

The term “comonomer” refers to olefin comonomers which are suitable forbeing polymerized with olefin monomers, such as ethylene or propylenemonomers. Comonomers may comprise but are not limited to aliphaticC₂-C₂₀ α-olefins. Examples of suitable aliphatic C₂-C₂₀ α-olefinsinclude ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene and 1-eicosene. In an embodiment, the comonomer is vinylacetate. The term “copolymer” refers to a polymer, which is made bylinking more than one type of monomer in the same polymer chain. Theterm “homopolymer” refers to a polymer which is made by linking olefinmonomers, in the absence of comonomers. The amount of comonomer can, insome embodiments, be from greater than 0 to about 12 wt % based on theweight of the polyolefin, including from greater than 0 to about 9 wt %and from greater than 0 to about 7 wt %. In some embodiments, thecomonomer content is greater than about 2 mol % of the final polymer,including greater than about 3 mol % and greater than about 6 mol %. Thecomonomer content may be less than or equal to about 30 mol %. Acopolymer can be a random or block (heterophasic) copolymer. In someembodiments, the polyolefin is a random copolymer of propylene andethylene.

In some aspects, the first polyolefin is selected from the groupconsisting of: an olefin homopolymer, a blend of homopolymers, acopolymer made using two or more olefins, a blend of copolymers eachmade using two or more olefins, and a combination of olefin homopolymersblended with copolymers made using two or more olefins. The olefin maybe selected from ethylene, propylene, 1-butene, 1-propene, 1-hexene,1-octene, and other higher 1-olefin. The first polyolefin may besynthesized using many different processes (e.g., using gas phase andsolution based using metallocene catalysis and Ziegler-Natta catalysis)and optionally using a catalyst suitable for polymerizing ethyleneand/or α-olefins. In some aspects, a metallocene catalyst may be used toproduce low density ethylene/α-olefin polymers.

In some aspects, the polyethylene used for the first polyolefin can beclassified into several types including, but not limited to, LDPE (LowDensity Polyethylene), LLDPE (Linear Low Density Polyethylene), and HDPE(High Density Polyethylene). In other aspects, the polyethylene can beclassified as Ultra High Molecular Weight (UHMW), High Molecular Weight(HMW), Medium Molecular Weight (MMW) and Low Molecular Weight (LMW). Instill other aspects, the polyethylene may be an ultra-low densityethylene elastomer.

In some aspects, the first polyolefin may include a LDPE/silanecopolymer or blend. In other aspects, the first polyolefin may bepolyethylene that can be produced using any catalyst known in the artincluding, but not limited to, chromium catalysts, Ziegler-Nattacatalysts, metallocene catalysts or post-metallocene catalysts.

In some aspects, the first polyolefin may have a molecular weightdistribution M_(w)/M_(n) of less than or equal to about 5, less than orequal to about 4, from about 1 to about 3.5, or from about 1 to about 3.

The first polyolefin may be present in an amount of from greater than 0to about 100 wt % of the composition. In some embodiments, the amount ofpolyolefin elastomer is from about 30 to about 70 wt %. In some aspects,the first polyolefin fed to an extruder can include from about 50 wt %to about 80 wt % of an ethylene/α-olefin copolymer, including from about60 wt % to about 75 wt % and from about 62 wt % to about 72 wt %.

The first polyolefin may have a melt viscosity in the range of fromabout 2,000 cP to about 50,000 cP as measured using a Brookfieldviscometer at a temperature of about 177° C. In some embodiments, themelt viscosity is from about 4,000 cP to about 40,000 cP, including fromabout 5,000 cP to about 30,000 cP and from about 6,000 cP to about18,000 cP.

The first polyolefin may have a melt index (T2), measured at 190° C.under a 2.16 kg load, of from about 20.0 g/10 min to about 3,500 g/10min, including from about 250 g/10 min to about 1,900 g/10 min and fromabout 300 g/10 min to about 1,500 g/10 min. In some aspects, the firstpolyolefin has a fractional melt index of from 0.5 g/10 min to about3,500 g/10 min.

In some aspects, the density of the first polyolefin is less than 0.90g/cm³, less than about 0.89 g/cm³, less than about 0.88 g/cm³, less thanabout 0.87 g/cm³, less than about 0.86 g/cm³, less than about 0.85g/cm³, less than about 0.84 g/cm³, less than about 0.83 g/cm³, less thanabout 0.82 g/cm³, less than about 0.81 g/cm³, or less than about 0.80g/cm³. In other aspects, the density of the first polyolefin may be fromabout 0.85 g/cm³to about 0.89 g/cm³, from about 0.85 g/cm³to about 0.88g/cm³, from about 0.84 g/cm³to about 0.88 g/cm³, or from about 0.83g/cm³to about 0.87 g/cm³. In still other aspects, the density is atabout 0.84 g/cm³, about 0.85 g/cm³, about 0.86 g/cm³, about 0.87 g/cm³,about 0.88 g/cm³, or about 0.89 g/cm³.

The percent crystallinity of the first polyolefin may be less than about60%, less than about 50%, less than about 40%, less than about 35%, lessthan about 30%, less than about 25%, or less than about 20%. The percentcrystallinity may be at least about 10%. In some aspects, thecrystallinity is in the range of from about 2% to about 60%.

Second Polyolefin

The second polyolefin can be a polyolefin elastomer including an olefinblock copolymer, an ethylene/α-olefin copolymer, a propylene/α-olefincopolymer, EPDM, EPM, or a mixture of two or more of any of thesematerials. Exemplary block copolymers include those sold under the tradenames INFUSE™ (the Dow Chemical Company) and SEPTON™ V-SERIES (KurarayCo., LTD.). Exemplary ethylene/α-olefin copolymers include those soldunder the trade names TAFMER™ (e.g., TAFMER DF710) (Mitsui Chemicals,Inc.) and ENGAGE™ (e.g., ENGAGE 8150) (the Dow Chemical Company).Exemplary propylene/α-olefin copolymers include those sold under thetrade name TAFMER™ XM grades (Mitsui Chemical Company) and VISTAMAXX™(e.g., VISTAMAXX 6102) (Exxon Mobil Chemical Company). The EPDM may havea diene content of from about 0.5 to about 10 wt %. The EPM may have anethylene content of 45 wt % to 75 wt %.

In some aspects, the second polyolefin is selected from the groupconsisting of: an olefin homopolymer, a blend of homopolymers, acopolymer made using two or more olefins, a blend of copolymers eachmade using two or more olefins, and a blend of olefin homopolymers withcopolymers made using two or more olefins. The olefin may be selectedfrom ethylene, propylene, 1-butene, 1-propene, 1-hexene, 1-octene, andother higher 1-olefin. The first polyolefin may be synthesized usingmany different processes (e.g., using gas phase and solution based usingmetallocene catalysis and Ziegler-Natta catalysis) and optionally usinga catalyst suitable for polymerizing ethylene and/or α-olefins. In someaspects, a metallocene catalyst may be used to produce low densityethylene/α-olefin polymers.

In some aspects, the second polyolefin may include a polypropylenehomopolymer, a polypropylene copolymer, a polyethylene-co-propylenecopolymer, or a mixture thereof. Suitable polypropylenes include but arenot limited to polypropylene obtained by homopolymerization of propyleneor copolymerization of propylene and an alpha-olefin comonomer. In someaspects, the second polyolefin may have a higher molecular weight and/ora higher density than the first polyolefin.

In some embodiments, the second polyolefin may have a molecular weightdistribution M_(w)/M_(n) of less than or equal to about 5, less than orequal to about 4, from about 1 to about 3.5, or from about 1 to about 3.

The second polyolefin may be present in an amount of from greater than 0wt % to about 100 wt % of the composition. In some embodiments, theamount of polyolefin elastomer is from about 30 wt % to about 70 wt %.In some embodiments, the second polyolefin fed to the extruder caninclude from about 10 wt % to about 50 wt % polypropylene, from about 20wt % to about 40 wt % polypropylene, or from about 25 wt % to about 35wt % polypropylene. The polypropylene may be a homopolymer or acopolymer.

The second polyolefin may have a melt viscosity in the range of fromabout 2,000 cP to about 50,000 cP as measured using a Brookfieldviscometer at a temperature of about 177° C. In some embodiments, themelt viscosity is from about 4,000 cP to about 40,000 cP, including fromabout 5,000 cP to about 30,000 cP and from about 6,000 cP to about18,000 cP.

The second polyolefin may have a melt index (T2), measured at 190° C.under a 2.16 kg load, of from about 20.0 g/10 min to about 3,500 g/10min, including from about 250 g/10 min to about 1,900 g/10 min and fromabout 300 g/10 min to about 1,500 g/10 min. In some embodiments, thepolyolefin has a fractional melt index of from 0.5 g/10 min to about3,500 g/10 min.

In some aspects, the density of the second polyolefin is less than 0.90g/cm³, less than about 0.89 g/cm³, less than about 0.88 g/cm³, less thanabout 0.87 g/cm³, less than about 0.86 g/cm³, less than about 0.85g/cm³, less than about 0.84 g/cm³, less than about 0.83 g/cm³, less thanabout 0.82 g/cm³, less than about 0.81 g/cm³, or less than about 0.80g/cm³. In other aspects, the density of the first polyolefin may be fromabout 0.85 g/cm³to about 0.89 g/cm³, from about 0.85 g/cm³to about 0.88g/cm³, from about 0.84 g/cm³to about 0.88 g/cm³, or from about 0.83g/cm³to about 0.87 g/cm³. In still other aspects, the density is atabout 0.84 g/cm³, about 0.85 g/cm³, about 0.86 g/cm³, about 0.87 g/cm³,about 0.88 g/cm³, or about 0.89 g/cm³.

The percent crystallinity of the second polyolefin may be less thanabout 60%, less than about 50%, less than about 40%, less than about35%, less than about 30%, less than about 25%, or less than about 20%.The percent crystallinity may be at least about 10%. In some aspects,the crystallinity is in the range of from about 2% to about 60%.

As noted, the silane-crosslinked polyolefin elastomer or blend, e.g., asemployed in combined sealing members 12 (see FIGS. 1, 2, 4 and 5),includes both the first polyolefin and the second polyolefin. The secondpolyolefin is generally used to modify the hardness and/orprocessability of the first polyolefin having a density less than 0.90g/cm³. In some aspects, more than just the first and second polyolefinsmay be used to form the silane-crosslinked polyolefin elastomer orblend. For example, in some aspects, one, two, three, four, or moredifferent polyolefins having a density less than 0.90 g/cm³, less than0.89 g/cm³, less than 0.88 g/cm³, less than 0.87 g/cm³, less than 0.86g/cm³, or less than 0.85 g/cm³ may be substituted and/or used for thefirst polyolefin. In some aspects, one, two, three, four, or moredifferent polyolefins, polyethylene-co-propylene copolymers may besubstituted and/or used for the second polyolefin.

The blend of the first polyolefin having a density less than 0.90 g/cm³and the second polyolefin having a crystallinity less than 40% is usedbecause the subsequent silane grafting and crosslinking of these firstand second polyolefin materials together are what form the core resinstructure in the final silane-crosslinked polyolefin elastomer. Althoughadditional polyolefins may be added to the blend of the silane-grafted,silane-crosslinkable, and/or silane-crosslinked polyolefin elastomer asfillers to improve and/or modify the Young's modulus as desired for thefinal product, any polyolefins added to the blend having a crystallinityequal to or greater than 40% are not chemically or covalentlyincorporated into the crosslinked structure of the finalsilane-crosslinked polyolefin elastomer.

In some aspects, the first and second polyolefins may further includeone or more TPVs and/or EPDM with or without silane graft moieties wherethe TPV and/or EPDM polymers are present in an amount of up to 20 wt %of the silane-crosslinked polyolefin elastomer/blend.

Grafting Initiator

A grafting initiator (also referred to as “a radical initiator” in thedisclosure) can be utilized in the grafting process of at least thefirst and second polyolefins by reacting with the respective polyolefinsto form a reactive species that can react and/or couple with the silanecrosslinker molecule. The grafting initiator can include halogenmolecules, azo compounds (e.g., azobisisobutyl), carboxylic peroxyacids,peroxyesters, peroxyketals, and peroxides (e.g., alkyl hydroperoxides,dialkyl peroxides, and diacyl peroxides). In some embodiments, thegrafting initiator is an organic peroxide selected from di-t-butylperoxide, t-butyl cumyl peroxide, dicumyl peroxide,2,5-dimethyl-2,5-di(t-butyl-peroxy)hexyne-3,1,3-bis(t-butyl-peroxy-isopropyl)benzene,n-butyl-4,4-bis(t-butyl-peroxy)valerate, benzoyl peroxide,t-butylperoxybenzoate, t-butylperoxy isopropyl carbonate, andt-butylperbenzoate, as well as bis(2-methylbenzoyl)peroxide,bis(4-methylbenzoyl)peroxide, t-butyl peroctoate, cumene hydroperoxide,methyl ethyl ketone peroxide, lauryl peroxide, tert-butyl peracetate,di-t-amyl peroxide, t-amyl peroxybenzoate,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane,α,α-bis(t-butylperoxy)-1,3-diisopropylbenzene,α,α-bis(t-butylpexoxy)-1,4-diisopropylbenzene,2,5-bis(t-butylperoxy)-2,5-dimethylhexane, and2,5-bis(t-butylperoxy)-2,5-dimethyl-3-hexyne and 2,4-dichlorobenzoylperoxide. Exemplary peroxides include those sold under the tradenameLUPEROX™ (available from Arkema, Inc.).

In some aspects, the grafting initiator is present in an amount of fromgreater than 0 wt % to about 2 wt % of the composition, including fromabout 0.15 wt % to about 1.2 wt % of the composition. The amount ofinitiator and silane employed may affect the final structure of thesilane grafted polymer (e.g., the degree of grafting in the graftedpolymer and the degree of crosslinking in the cured polymer). In someaspects, the reactive composition contains at least 100 ppm ofinitiator, or at least 300 ppm of initiator. The initiator may bepresent in an amount from 300 ppm to 1500 ppm, or from 300 ppm to 2000ppm. The silane:initiator weight ratio may be from about 20:1 to 400:1,including from about 30:1 to about 400:1, from about 48:1 to about350:1, and from about 55:1 to about 333:1.

The grafting reaction can be performed under conditions that optimizegrafts onto the interpolymer backbone while minimizing side reactions(e.g., the homopolymerization of the grafting agent). The graftingreaction may be performed in a melt, in solution, in a solid-state,and/or in a swollen-state. The silanation may be performed in awide-variety of equipment (e.g., twin screw extruders, single screwextruders, Brabenders, internal mixers such as Banbury mixers, and batchreactors). In some embodiments, the polyolefin, silane, and initiatorare mixed in the first stage of an extruder. The melt temperature (i.e.,the temperature at which the polymer starts melting and starts to flow)may be from about 120° C. to about 260° C., including from about 130° C.to about 250° C.

Silane Crosslinker

A silane crosslinker can be used to covalently graft silane moietiesonto the first and second polyolefins and the silane crosslinker mayinclude alkoxysilanes, silazanes, siloxanes, or a combination thereof.The grafting and/or coupling of the various potential silanecrosslinkers or silane crosslinker molecules is facilitated by thereactive species formed by the grafting initiator reacting with therespective silane crosslinker.

In some aspects, the silane crosslinker is a silazane where the silazanemay include, for example, hexamethyldisilazane (HMDS) orBis(trimethylsilyl)amine. In some aspects, the silane crosslinker is asiloxane where the siloxane may include, for example,polydimethylsiloxane (PDMS) and octamethylcyclotetrasiloxane.

In some aspects, the silane crosslinker is an alkoxysilane. As usedherein, the term “alkoxysilane” refers to a compound that comprises asilicon atom, at least one alkoxy group and at least one other organicgroup, wherein the silicon atom is bonded with the organic group by acovalent bond. Preferably, the alkoxysilane is selected fromalkylsilanes; acryl-based silanes; vinyl-based silanes; aromaticsilanes; epoxy-based silanes; amino-based silanes and amines thatpossess —NH₂, —NHCH₃ or —N(CH₃)₂; ureide-based silanes; mercapto-basedsilanes; and alkoxysilanes which have a hydroxyl group (i.e., —OH). Anacryl-based silane may be selected from the group comprisingbeta-acryloxyethyl trimethoxysilane; beta-acryloxy propyltrimethoxysilane; gamma-acryloxyethyl trimethoxysilane;gamma-acryloxypropyl trimethoxysilane; beta-acryloxyethyltriethoxysilane; beta-acryloxypropyl triethoxysilane;gamma-acryloxyethyl triethoxysilane; gamma-acryloxypropyltriethoxysilane; beta-methacryloxyethyl trimethoxysilane;beta-methacryloxypropyl trimethoxysilane; gamma-methacryloxyethyltrimethoxysilane; gamma-methacryloxypropyl trimethoxysilane;beta-methacryloxyethyl triethoxysilane; beta-methacryloxypropyltriethoxysilane; gamma-methacryloxyethyl triethoxysilane;gamma-methacryloxypropyl triethoxysilane; 3-methacryloxypropylmethyldiethoxysilane. A vinyl-based silane may be selected from the groupcomprising vinyl trimethoxysilane; vinyl triethoxysilane; p-styryltrimethoxysilane; methylvinyldimethoxysilane;vinyldimethylmethoxysilane; divinyldimethoxysilane;vinyltris(2-methoxyethoxy)silane; andvinylbenzylethylenediaminopropyltrimethoxysilane. An aromatic silane maybe selected from phenyltrimethoxysilane and phenyltriethoxysilane. Anepoxy-based silane may be selected from the group comprising3-glycydoxypropyl trimethoxysilane; 3-glycydoxypropylmethyldiethoxysilane; 3-glycydoxypropyl triethoxysilane;2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, andglycidyloxypropylmethyldimethoxysilane. An amino-based silane may beselected from the group comprising 3-aminopropyl triethoxysilane;3-aminopropyl trimethoxysilane; 3-aminopropyldimethyl ethoxysilane;3-aminopropylmethyldiethoxysilane; 4-aminobutyltriethoxysilane;3-aminopropyldiisopropyl ethoxysilane;1-amino-2-(dimethylethoxysilyl)propane;(aminoethylamino)-3-isobutyldimethyl methoxysilane;N-(2-aminoethyl)-3-aminoisobutylmethyl dimethoxysilane;(aminoethylaminomethyl)phenetyl trimethoxysilane;N-(2-aminoethyl)-3-aminopropylmethyl dimethoxysilane;N-(2-aminoethyl)-3-aminopropyl trimethoxysilane;N-(2-aminoethyl)-3-aminopropyl triethoxysilane;N-(6-aminohexyl)aminomethyl trimethoxysilane;N-(6-aminohexyl)aminomethyl trimethoxysilane;N-(6-aminohexyl)aminopropyl trimethoxysilane;N-(2-aminoethyl)-1,1-aminoundecyl trimethoxysilane; 1,1-aminoundecyltriethoxysilane; 3-(m-aminophenoxy)propyl trimethoxysilane;m-aminophenyl trimethoxysilane; p-aminophenyl trimethoxysilane;(3-trimethoxysilylpropyl)diethylenetriamine; N-methylaminopropylmethyldimethoxysilane; N-methylaminopropyl trimethoxysilane;dimethylaminomethyl ethoxysilane;(N,N-dimethylaminopropyl)trimethoxysilane;(N-acetylglycysil)-3-aminopropyl trimethoxysilane,N-phenyl-3-aminopropyltrimethoxysilane,N-phenyl-3-aminopropyltriethoxysilane,phenylaminopropyltrimethoxysilane,aminoethylaminopropyltrimethoxysilane, andaminoethylaminopropylmethyldimethoxysilane. A ureide-based silane may be3-ureidepropyl triethoxysilane. A mercapto-based silane may be selectedfrom the group comprising 3-mercaptopropylmethyl dimethoxysilane,3-mercaptopropyl trimethoxysilane, and 3-mercaptopropyl triethoxysilane.An alkoxysilane having a hydroxyl group may be selected from the groupcomprising hydroxymethyl triethoxysilane;N-(hydroxyethyl)-N-methylaminopropyl trimethoxysilane;bis(2-hydroxyethyl)-3-aminopropyl triethoxysilane;N-(3-triethoxysilylpropyl)-4-hydroxy butylamide;1,1-(triethoxysilyl)undecanol; triethoxysilyl undecanol; ethylene glycolacetal; and N-(3-ethoxysilylpropyl)gluconamide.

In some aspects, the alkylsilane may be expressed with a generalformula: R_(n)Si(OR′)_(4-n) wherein: n is 1, 2 or 3; R is a C₁₋₂₀ alkylor a C₂₋₂₀ alkenyl; and R′ is an C₁₋₂₀ alkyl. The term “alkyl” by itselfor as part of another substituent, refers to a straight, branched orcyclic saturated hydrocarbon group joined by single carbon-carbon bondshaving 1 to 20 carbon atoms, for example 1 to 10 carbon atoms, forexample 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. When asubscript is used herein following a carbon atom, the subscript refersto the number of carbon atoms that the named group may contain. Thus,for example, C₁₋₆ alkyl means an alkyl of one to six carbon atoms.Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl, f-butyl, 2-methylbutyl, pentyl, iso-amyl and itsisomers, hexyl and its isomers, heptyl and its isomers, octyl and itsisomer, decyl and its isomer, dodecyl and its isomers. The term“C₂₋₂₀alkenyl” by itself or as part of another substituent, refers to anunsaturated hydrocarbyl group, which may be linear, or branched,comprising one or more carbon-carbon double bonds having 2 to 20 carbonatoms. Examples of C₂₋₆ alkenyl groups are ethenyl, 2-propenyl,2-butenyl, 3-butenyl, 2-pentenyl and its isomers, 2-hexenyl and itsisomers, 2,4-pentadienyl and the like.

In some aspects, the alkylsilane may be selected from the groupcomprising methyltrimethoxysilane; methyltriethoxysilane;ethyltrimethoxysilane; ethyltriethoxysilane; propyltrimethoxysilane;propyltriethoxysilane; hexyltrimethoxysilane; hexyltriethoxysilane;octyltrimethoxysilane; octyltriethoxysilane; decyltrimethoxysilane;decyltriethoxysilane; dodecyltrimethoxysilane: dodecyltriethoxysilane;tridecyltrimethoxysilane; dodecyltriethoxysilane;hexadecyltrimethoxysilane; hexadecyltriethoxysilane;octadecyltrimethoxysilane; octadecyltriethoxysilane,trimethylmethoxysilane, methylhydrodimethoxysilane,dimethyldimethoxysilane, diisopropyldimethoxysilane,diisobutyldimethoxysilane, isobutyltrimethoxysilane,n-butyltrimethoxysilane, n-butylmethyldimethoxysilane,phenyltrimethoxysilane, phenyltrimethoxysilane,phenylmethyldimethoxysilane, triphenylsilanol, n-hexyltrimethoxysilane,n-octyltrimethoxysilane, isooctyltrimethoxysilane,decyltrimethoxysilane, hexadecyltrimethoxysilane,cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane,dicyclopentyldimethoxysilane, tert-butylethyldimethoxysilane,tert-butylpropyldimethoxysilane, dicyclohexyldimethoxysilane, and acombination thereof.

In some aspects, the alkylsilane compound may be selected fromtriethoxyoctylsilane, trimethoxyoctylsilane, and a combination thereof.

Additional examples of silanes that can be used as silane crosslinkersinclude, but are not limited to, those of the general formulaCH₂═CR—(COO)_(x)(C_(n)H_(2n))_(y)SiR′₃, wherein R is a hydrogen atom ormethyl group; x is 0 or 1; y is 0 or 1; n is an integer from 1 to 12;each R′ can be an organic group and may be independently selected froman alkoxy group having from 1 to 12 carbon atoms (e.g., methoxy, ethoxy,butoxy), aryloxy group (e.g., phenoxy), araloxy group (e.g., benzyloxy),aliphatic acyloxy group having from 1 to 12 carbon atoms (e.g.,formyloxy, acetyloxy, propanoyloxy), amino or substituted amino groups(e.g., alkylamino, arylamino), or a lower alkyl group having 1 to 6carbon atoms. x and y may both equal 1. In some aspects, no more thanone of the three R′ groups is an alkyl. In other aspects, not more thantwo of the three R′ groups is an alkyl.

Any silane or mixture of silanes known in the art that can effectivelygraft to and crosslink an olefin polymer can be used in the practice ofthe present disclosure. In some aspects, the silane crosslinker caninclude, but is not limited to, unsaturated silanes which include anethylenically unsaturated hydrocarbyl group (e.g., a vinyl, allyl,isopropenyl, butenyl, cyclohexenyl or a gamma-(meth)acryloxy allylgroup) and a hydrolyzable group (e.g., a hydrocarbyloxy,hydrocarbonyloxy, or hydrocarbylamino group). Non-limiting examples ofhydrolyzable groups include, but are not limited to, methoxy, ethoxy,formyloxy, acetoxy, proprionyloxy, and alkyl, or arylamino groups. Inother aspects, the silane crosslinkers are unsaturated alkoxy silaneswhich can be grafted onto the polymer. In still other aspects,additional exemplary silane crosslinkers include vinyltrimethoxysilane,vinyltriethoxysilane, 3-(trimethoxysilyl)propyl methacrylategamma-(meth)acryloxypropyl trimethoxysilane), and mixtures thereof.

The silane crosslinker may be present in the silane-grafted polyolefinelastomer in an amount of from greater than 0 wt % to about 10 wt %,including from about 0.5 wt % to about 5 wt %. The amount of silanecrosslinker may be varied based on the nature of the olefin polymer, thesilane itself, the processing conditions, the grafting efficiency, theapplication, and other factors. The amount of silane crosslinker may beat least 2 wt %, including at least 4 wt % or at least 5 wt %, based onthe weight of the reactive composition. In other aspects, the amount ofsilane crosslinker may be at least 10 wt %, based on the weight of thereactive composition. In still other aspects, the silane crosslinkercontent is at least 1% based on the weight of the reactive composition.In some embodiments, the silane crosslinker fed to the extruder mayinclude from about 0.5 wt % to about 10 wt % of silane monomer, fromabout 1 wt % to about 5 wt % silane monomer, or from about 2 wt % toabout 4 wt % silane monomer.

Condensation Catalyst

A condensation catalyst can facilitate both the hydrolysis andsubsequent condensation of the silane grafts on the silane-graftedpolyolefin elastomer to form crosslinks. In some aspects, thecrosslinking can be aided by the use of an electron beam radiation. Insome aspects, the condensation catalyst can include, for example,organic bases, carboxylic acids, and organometallic compounds (e.g.,organic titanates and complexes or carboxylates of lead, cobalt, iron,nickel, zinc, and tin). In other aspects, the condensation catalyst caninclude fatty acids and metal complex compounds such as metalcarboxylates; aluminum triacetyl acetonate, iron triacetyl acetonate,manganese tetraacetyl acetonate, nickel tetraacetyl acetonate, chromiumhexaacetyl acetonate, titanium tetraacetyl acetonate and cobalttetraacetyl acetonate; metal alkoxides such as aluminum ethoxide,aluminum propoxide, aluminum butoxide, titanium ethoxide, titaniumpropoxide and titanium butoxide; metal salt compounds such as sodiumacetate, tin octylate, lead octylate, cobalt octylate, zinc octylate,calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltindioctoate, dibutyltin dilaurate, dibutyltin maleate and dibutyltindi(2-ethylhexanoate); acidic compounds such as formic acid, acetic acid,propionic acid, p-toluenesulfonic acid, trichloroacetic acid, phosphoricacid, monoalkylphosphoric acid, dialkylphosphoric acid, phosphate esterof p-hydroxyethyl (meth)acrylate, monoalkylphosphorous acid anddialkylphosphorous acid; acids such as p-toluenesulfonic acid, phthalicanhydride, benzoic acid, benzenesulfonic acid, dodecylbenzenesulfonicacid, formic acid, acetic acid, itaconic acid, oxalic acid and maleicacid, ammonium salts, lower amine salts or polyvalent metal salts ofthese acids, sodium hydroxide, lithium chloride; organometal compoundssuch as diethyl zinc and tetra(n-butoxy)titanium; and amines such asdicyclohexylamine, triethylamine, N,N-dimethylbenzylamine,N,N,N′,N′-tetramethyl-1,3-butanediamine, diethanolamine, triethanolamineand cyclohexylethylamine. In still other aspects, the condensationcatalyst can include ibutyltindilaurate, dioctyltinmaleate,dibutyltindiacetate, dibutyltindioctoate, stannous acetate, stannousoctoate, lead naphthenate, zinc caprylate, and cobalt naphthenate.Depending on the desired final material properties of thesilane-crosslinked polyolefin elastomer or blend, a single condensationcatalyst or a mixture of condensation catalysts may be utilized. Thecondensation catalyst(s) may be present in an amount of from about 0.01wt % to about 1.0 wt5, including from about 0.25 wt % to about 8 wt %,based on the total weight of the silane-grafted polyolefinelastomer/blend composition.

In some aspects, a crosslinking system can include and use one or all ofa combination of radiation, heat, moisture, and additional condensationcatalyst. In some aspects, the condensation catalyst may be present inan amount of from 0.25 wt % to 8 wt %. In other aspects, thecondensation catalyst may be included in an amount of from about 1 wt %to about 10 wt %, or from about 2 wt % to about 5 wt %.

Foaming Agent

According to some embodiments, the foaming agent can be a chemicalfoaming agent (e.g., organic or inorganic foaming agent) and/or aphysical foaming (e.g., gases and volatile low weight molecules) that isadded to the silane-grafted polyolefin elastomer and condensationcatalyst blend during the extrusion and/or molding process to produce afoamed (sponge or dynamic) silane-crosslinked polyolefin elastomer.

In some aspects, an endothermic blowing (foaming) agent may be used thatcan include, for example, sodium bicarbonate and/or citric acid and itssalts or derivatives. Exemplary citric acid foaming agents include thosesold under the trade name HYDROCEROL® that includes a mixture of zincstearate, polyethylene glycol, and a citric acid or citric acidderivative. The desired decomposition temperature for the endothermicblowing (foaming) agent may be from about 160° C. to about 200° C., orabout 175° C., about 180° C., about 185° C., about 190° C., or about195° C.

Organic foaming agents that may be used can include, for example, azocompounds, such as azodicarbonamide (ADCA), barium azodicarboxylate,azobisisobutyronitrile (AIBN), azocyclohexylnitrile, andazodiaminobenzene, N-nitroso compounds, such asN,N′-dinitrosopentamethylenetetramine (DPT),N,N′-dimethyl-N,N′-dinitrosoterephthalamide, andtrinitrosotrimethyltriamine, hydrazide compounds, such as4,4′-oxybis(benzenesulfonylhydrazide) (OBSH), paratoluenesulfonylhydrazide, diphenylsulfone-3,3′-disulfonylhydrazide,2,4-toluenedisulfonylhydrazide, p,p-bis(benzenesulfonylhydrazide)ether,benzene-1,3-disulfonylhydrazide, and allylbis(sulfonylhydrazide),semicarbazide compounds, such as p-toluilenesulfonylsemicarbazide, and4,4′-oxybis(benzenesulfonylsemicarbazide), alkane fluorides, such astrichloromonofluoromethane, and dichloromonofluoromethane, and triazolecompounds, such as 5-morpholyl-1,2,3,4-thiatriazole, and other knownorganic foaming agents. Preferably, azo compounds and N-nitrosocompounds are used. Further preferably, azodicarbonamide (ADCA) andN,N′-dinitrosopentamethylenetetramine (DPT) are used. The organicfoaming agents listed above may be used alone or in any combination oftwo or more.

The decomposition temperature and amount of organic foaming agent usedcan have important consequences on the density and material propertiesof the foamed silane-crosslinked polyolefin elastomer. In some aspects,the organic foaming agent has a decomposition temperature of from about150° C. to about 210° C. The organic foaming agent can be used in anamount of from about 0.1 wt % to about 40 wt %, from about 5 wt % toabout 30 wt %, from about 5 wt % to about 20 wt %, from about 10 wt % toabout 30 wt %, or from about 1 wt % to about 10 wt % based on the totalweight of the polymer blend. If the organic foaming agent has adecomposition temperature lower than 150° C., early foaming may occurduring compounding. Meanwhile, if the organic foaming agent has adecomposition temperature higher than 210° C., it may take longer, e.g.,greater than 15 minutes, to mold the foam, resulting in lowproductivity. Additional foaming agents may include any compound whosedecomposition temperature is within the range defined above.

The inorganic foaming agents that may be used include, for example,hydrogen carbonate, such as sodium hydrogen carbonate, and ammoniumhydrogen carbonate, carbonate, such as sodium carbonate, and ammoniumcarbonate, nitrite, such as sodium nitrite, and ammonium nitrite,borohydride, such as sodium borohydride, and other known inorganicfoaming agents, such as azides. In some aspect, hydrogen carbonate maybe used. In other aspects, sodium hydrogen carbonate may be used. Theinorganic foaming agents listed above may be used alone or in anycombination of two or more. The inorganic foaming agent can be used inan amount of from about 0.1 wt % to about 40 wt %, from about 5 wt % toabout 30 wt %, from about 5 wt % to about 20 wt %, from about 10 wt % toabout 30 wt %, or from about 1 wt % to about 10 wt % based on the totalweight of the polymer blend. Physical blowing agents that may be usedinclude, for example, supercritical carbon dioxide, supercriticalnitrogen, butane, pentane, isopentane, cyclopentane. In some aspects,various minerals or inorganic compounds (e.g., talc) may be used as anucleating agent for the supercritical fluid. The physical foaming agentcan be used in an amount of from about 0.1 wt % to about 40 wt %, fromabout 5 wt % to about 30 wt %, from about 5 wt % to about 20 wt %, fromabout 10 wt % to about 30 wt %, or from about 1 wt % to about 10 wt %based the total weight of the polymer blend.

Blowing Agent

According to some embodiments, the foaming agent can be a chemicalfoaming agent (e.g., organic or inorganic foaming agent) and/or aphysical foaming (e.g., gases and volatile low weight molecules) that isadded to the silane-grafted polyolefin elastomer and condensationcatalyst blend during the extrusion and/or molding process to produce afoamed (micro-dense) silane-crosslinked polyolefin elastomer.

In some aspects, the foaming agent may a physical foaming agentincluding a microencapsulated foaming agent, otherwise referred to inthe art as a microencapsulated blowing agent (MEBA). MEBAs include afamily of physical foaming agents that are defined as a thermoexpandable microsphere which is formed by the encapsulation of avolatile hydrocarbon into an acrylic copolymer shell. When the acryliccopolymer shell expands, the volatile hydrocarbon (e.g., butane) createsa foam in the silane-crosslinkable polyolefin elastomer and reduces itsweight. In some aspects, the MEBAs have an average particle size of fromabout 20 μm to about 30 μm. Exemplary MEBAs include those sold under thetrade name MATSUMOTO F-AC170D. In some aspects, MEBA's may be used incombination with other foaming agents including organic and inorganicfoaming agents.

Organic foaming agents that may be used can include, for example, azocompounds, such as azodicarbonamide (ADCA), barium azodicarboxylate,azobisisobutyronitrile (AIBN), azocyclohexylnitrile, andazodiaminobenzene, N-nitroso compounds, such asN,N′-dinitrosopentamethylenetetramine (DPT),N,N′-dimethyl-N,N′-dinitrosoterephthalamide, andtrinitrosotrimethyltriamine, hydrazide compounds, such as4,4′-oxybis(benzenesulfonylhydrazide)(OBSH), paratoluenesulfonylhydrazide, diphenylsulfone-3,3′-disulfonylhydrazide,2,4-toluenedisulfonylhydrazide, p,p-bis(benzenesulfonylhydrazide)ether,benzene-1,3-disulfonylhydrazide, and allylbis(sulfonylhydrazide),semicarbazide compounds, such as p-toluilenesulfonylsemicarbazide, and4,4′-oxybis(benzenesulfonylsemicarbazide), alkane fluorides, such astrichloromonofluoromethane, and dichloromonofluoromethane, and triazolecompounds, such as 5-morpholyl-1,2,3,4-thiatriazole, and other knownorganic foaming agents. Preferably, azo compounds and N-nitrosocompounds are used. Further preferably, azodicarbonamide (ADCA) andN,N′-dinitrosopentamethylenetetramine (DPT) are used. The organicfoaming agents listed above may be used alone or in any combination oftwo or more.

The decomposition temperature and amount of organic foaming agent usedcan have important consequences on the density and material propertiesof the foamed silane-crosslinker polyolefin elastomer. In some aspects,the organic foaming agent has a decomposition temperature of from about150° C. to about 210° C. The organic foaming agent can be used in anamount of from about 0.1 wt % to about 40 wt %, from about 5 wt % toabout 30 wt %, from about 5 wt % to about 20 wt %, from about 10 wt % toabout 30 wt %, or from about 1 wt % to about 10 wt % based on the totalweight of the polymer blend. If the organic foaming agent has adecomposition temperature lower than 150° C., early foaming may occurduring compounding. Meanwhile, if the organic foaming agent has adecomposition temperature higher than 210° C., it may take longer, e.g.,greater than 15 minutes, to mold the foam, resulting in lowproductivity. Additional foaming agents may include any compound whosedecomposition temperature is within the range defined above.

The inorganic foaming agents that may be used include, for example,hydrogen carbonate, such as sodium hydrogen carbonate, and ammoniumhydrogen carbonate, carbonate, such as sodium carbonate, and ammoniumcarbonate, nitrite, such as sodium nitrite, and ammonium nitrite,borohydride, such as sodium borohydride, and other known inorganicfoaming agents, such as azides. In some aspect, hydrogen carbonate maybe used. In other aspects, sodium hydrogen carbonate may be used. Theinorganic foaming agents listed above may be used alone or in anycombination of two or more. The inorganic foaming agent can be used inan amount of from about 0.1 wt % to about 40 wt %, from about 5 wt % toabout 30 wt %, from about 5 wt % to about 20 wt %, from about 10 wt % toabout 30 wt %, or from about 1 wt % to about 10 wt % based on the totalweight of the polymer blend. Physical blowing agents that may be usedinclude, for example, supercritical carbon dioxide, supercriticalnitrogen, butane, pentane, isopentane, cyclopentane. The physicalfoaming agent can be used in an amount of from about 0.1 wt % to about40 wt %, from about 5 wt % to about 30 wt %, from about 5 wt % to about20 wt %, from about 10 wt % to about 30 wt %, or from about 1 wt % toabout 10 wt % based the total weight of the polymer blend.

Optional Additional Components

The silane-crosslinked polyolefin elastomer may optionally include oneor more fillers. The filler(s) may be extruded with the silane-graftedpolyolefin and in some aspects may include additional polyolefins havinga crystallinity greater than 20%, greater than 30%, greater than 40%, orgreater than 50%. In some aspects, the filler(s) may include metaloxides, metal hydroxides, metal carbonates, metal sulfates, metalsilicates, clays, talcs, carbon black, and silicas. Depending on theapplication and/or desired properties, these materials may be fumed orcalcined.

With further regard to the filler(s), the metal of the metal oxide,metal hydroxide, metal carbonate, metal sulfate, or metal silicate maybe selected from alkali metals (e.g., lithium, sodium, potassium,rubidium, caesium, and francium); alkaline earth metals (e.g.,beryllium, magnesium, calcium, strontium, barium, and radium);transition metals (e.g., zinc, molybdenum, cadmium, scandium, titanium,vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium,zirconium, niobium, technetium, ruthernium, rhodium, palladium, silver,hafnium, taltalum, tungsten, rhenium, osmium, indium, platinum, gold,mercury, rutherfordium, dubnium, seaborgium, bohrium, hassium, andcopernicium); post-transition metals (e.g., aluminum, gallium, indium,tin, thallium, lead, bismuth, and polonium); lanthanides (e.g.,lanthanum, cerium, praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, and lutetium); actinides (e.g., actinium, thorium,protactinium, uranium, neptunium, plutonium, americium, curium,berkelium, californium, einsteinium, fermium, mendelevium, nobelium, andlawrencium); germanium; arsenic; antimony; and astatine.

The filler(s) of the silane-crosslinked polyolefin elastomer or blendmay be present in an amount of from greater than 0 wt % to about 50 wt%, including from about 1 wt % to about 20 wt % and from about 3 wt % toabout 10 wt %.

The silane-crosslinked polyolefin elastomer and/or the respectivearticles formed (e.g., combined sealing members 12) may also includewaxes (e.g., paraffin waxes, microcrystalline waxes, HDPE waxes, LDPEwaxes, thermally degraded waxes, byproduct polyethylene waxes,optionally oxidized Fischer-Tropsch waxes, and functionalized waxes). Insome embodiments, the wax(es) are present in an amount of from about 0wt % to about 10 wt %.

Tackifying resins (e.g., aliphatic hydrocarbons, aromatic hydrocarbons,modified hydrocarbons, terpens, modified terpenes, hydrogenatedterpenes, rosins, rosin derivatives, hydrogenated rosins, and mixturesthereof) may also be included in the silane-crosslinked polyolefinelastomer/blend. The tackifying resins may have a ring and ballsoftening point in the range of from 70° C. to about 150° C. and aviscosity of less than about 3,000 cP at 177° C. In some aspects, thetackifying resin(s) are present in an amount of from about 0 wt % toabout 10 wt %.

In some aspects, the silane-crosslinked polyolefin elastomer may includeone or more oils. Non-limiting types of oils include white mineral oilsand naphthenic oils. In some embodiments, the oil(s) are present in anamount of from about 0 wt % to about 10 wt %.

In some aspects, the silane-crosslinked polyolefin elastomer may includeone or more filler polyolefins having a crystallinity greater than 20%,greater than 30%, greater than 40%, or greater than 50%. The fillerpolyolefin may include polypropylene, poly(ethylene-co-propylene),and/or other ethylene/α-olefin copolymers. In some aspects, the use ofthe filler polyolefin may be present in an amount of from about 5 wt %to about 60 wt %, from about 10 wt % to about 50 wt %, from about 20 wt% to about 40 wt %, or from about 5 wt % to about 20 wt %. The additionof the filler polyolefin may increase the Young's modulus by at least10%, by at least 25%, or by at least 50% for the finalsilane-crosslinked polyolefin elastomer.

In some aspects, the silane-crosslinked polyolefin elastomer of thepresent disclosure may include one or more stabilizers (e.g.,antioxidants). The silane-crosslinked polyolefin elastomer may betreated before grafting, after grafting, before crosslinking, and/orafter crosslinking. Other additives may also be included. Non-limitingexamples of additives include antistatic agents, dyes, pigments, UVlight absorbers, nucleating agents, fillers, slip agents, plasticizers,fire retardants, lubricants, processing aides, smoke inhibitors,anti-blocking agents, and viscosity control agents. The antioxidant(s)may be present in an amount of less than 0.5 wt %, including less than0.2 wt % of the composition.

Method for Making the Silane-Grafted Polyolefin Elastomer

The synthesis/production of the dense, micro-dense and dynamicsilane-crosslinked polyolefin elastomers of the disclosure, e.g., asemployed in the combined sealing members 12, may be performed bycombining the respective components in one extruder using a single-stepMonosil process or in two extruders using a two-step Sioplas processwhich eliminates the need for additional steps of mixing and shippingrubber compounds prior to extrusion.

Referring now to FIG. 7, the general chemical process used during boththe single-step

Monosil process and two-step Sioplas process used to synthesize thesilane-crosslinked polyolefin elastomers is provided. The process startswith a grafting step that includes initiation from a grafting initiatorfollowed by propagation and chain transfer with the first and secondpolyolefins. The grafting initiator, in some aspects a peroxide or azocompound, homolytically cleaves to form two radical initiator fragmentsthat transfer to one of the first and second polyolefins chains througha propagation step. The free radical, now positioned on the first orsecond polyolefin chain, can then transfer to a silane molecule and/oranother polyolefin chain. Once the initiator and free radicals areconsumed, the silane grafting reaction for the first and secondpolyolefins is complete.

Still referring to FIG. 7, once the silane grafting reaction iscomplete, a mixture of stable first and second silane-graftedpolyolefins is produced. A crosslinking catalyst may then be added tothe first and second silane-grafted polyolefins to form thesilane-grafted polyolefin elastomer. The crosslinking catalyst may firstfacilitate the hydrolysis of the silyl group grafted onto the polyolefinbackbones to form reactive silanol groups. The silanol groups may thenreact with other silanol groups on other polyolefin molecules to form acrosslinked network of elastomeric polyolefin polymer chains linkedtogether through siloxane linkages. The density of silane crosslinksthroughout the silane-grafted polyolefin elastomer can influence thematerial properties exhibited by the elastomer.

Referring now to FIGS. 8 and 9A, a method 300 for making a combinedseal, such as the combined sealing member 12, using the two-step Sioplasprocess is shown. The method 300 may begin with a step 304 that includesextruding (e.g., with a twin screw extruder 182) the first polyolefin170 having a density less than 0.86 g/cm³, the second polyolefin 174,and a silan cocktail 178 including the silane crosslinker (e.g.,vinyltrimethoxy silane, VTMO) and the grafting initiator (e.g. dicumylperoxide) together to form a silane-grafted polyolefin blend. The firstpolyolefin 170 and second polyolefin 174 may be added to a reactive twinscrew extruder 182 using an addition hopper 186. The silan cocktail 178may be added to the twin screws 190 further down the extrusion line tohelp promote better mixing with the first and second polyolefin 170, 174blend. A forced volatile organic compound (VOC) vacuum 194 may be usedon the reactive twin screw extruder 182 to help maintain a desiredreaction pressure. The twin screw extruder 182 is considered reactivebecause the radical initiator and silane crosslinker are reacting withand forming new covalent bonds with both the first and secondpolyolefins 170, 174. The melted silane-grafted polyolefin blend canexit the reactive twin screw extruder 182 using a gear pump 198 thatinjects the molten silane-grafted polyolefin blend into a waterpelletizer 202 that can form a pelletized silane-grafted polyolefinblend 206. In some aspects, the molten silane-grafted polyolefin blendmay be extruded into pellets, pillows, or any other configuration priorto the incorporation of the condensation catalyst 210 (see FIG. 9B) andformation of the final article.

The reactive twin screw extruder 182 can be configured to have aplurality of different temperature zones (e.g., Z0-Z12 as shown in FIG.9A) that extend for various lengths of the twin screw extruder 182. Insome aspects, the respective temperature zones may have temperaturesranging from about room temperature to about 180° C., from about 120° C.to about 170° C., from about 120° C. to about 160° C., from about 120°C. to about 150° C., from about 120° C. to about 140° C., from about120° C. to about 130° C., from about 130° C. to about 170° C., fromabout 130° C. to about 160° C., from about 130° C. to about 150° C.,from about 130° C. to about 140° C., from about 140° C. to about 170°C., from about 140° C. to about 160° C., from about 140° C. to about150° C., from about 150° C. to about 170° C., and from about 150° C. toabout 160° C. In some aspects, Z0 may have a temperature from about 60°C. to about 110° C. or no cooling; Z1 may have a temperature from about120° C. to about 130° C.; Z2 may have a temperature from about 140° C.to about 150° C.; Z3 may have a temperature from about 150° C. to about160° C.; Z4 may have a temperature from about 150° C. to about 160° C.;Z5 may have a temperature from about 150° C. to about 160° C.; Z6 mayhave a temperature from about 150° C. to about 160° C.; and Z7-Z12 mayhave a temperature from about 150° C. to about 160° C.

In some aspects, the number average molecular weight of thesilane-grafted polyolefin elastomers may be in the range of from about4,000 g/mol to about 30,000 g/mol, including from about 5,000 g/mol toabout 25,000 g/mol and from about 6,000 g/mol to about 14,000 g/mol. Theweight average molecular weight of the grafted polymers may be fromabout 8,000 g/mol to about 60,000 g/mol, including from about 10,000g/mol to about 30,000 g/mol.

Referring now to FIGS. 8 and 9B, the method 300 next includes a step 308of extruding the silane-grafted polyolefin blend 206 and thecondensation catalyst 210 together to form a silane-crosslinkablepolyolefin blend 212. In some aspects, one or more optional additives214 may be added with the silane-grafted polyolefin blend 206 and thecondensation catalyst 210 to adjust the final material properties of thesilane-crosslinked polyolefin olefin blend. In embodiments for formingdynamic and micro-dense silane-crosslinked polyolefin blends, theadditives 214 can comprise foaming agents, as detailed above. In step308, the silane-grafted polyolefin blend 206 is mixed with a silanolforming condensation catalyst 210 to form reactive silanol groups on thesilane grafts that can subsequently crosslink when exposed to humidityand/or heat. In some aspects, the condensation catalyst is AMBICAT™LE4472 and can include a mixture of sulfonic acid, antioxidant, processaide, and carbon black for coloring where the ambient moisture issufficient for this condensation catalyst to crosslink thesilane-crosslinkable polyolefin blend over a longer time period (e.g.,about 48 hours). The silane-grafted polyolefin blend 206 and thecondensation catalyst 210 may be added to a reactive single screwextruder 218 using an addition hopper and an addition gear pump 226. Thecombination of the silane-grafted polyolefin blend 206 and thecondensation catalyst 210, and in some aspects one or more optionaladditives 214, may be added to a single screw 222 of the reactive singlescrew extruder 218. The single screw extruder 218 is considered reactivebecause crosslinking can begin as soon as the silane-grafted polyolefinblend 206 and the condensation catalyst 210 are melted and combinedtogether to mix the condensation catalyst 210 thoroughly and evenlythroughout the melted silane-grafted polyolefin blend 206. The meltedsilane-crosslinkable polyolefin blend 212 can exit the reactive singlescrew extruder 218 through a die that can inject the moltensilane-crosslinkable polyolefin blend into an uncured combined sealingelement.

During step 308, as the silane-grafted polyolefin blend 206 is extrudedtogether with the condensation catalyst 210 to form thesilane-crosslinkable polyolefin blend 212, a certain amount ofcrosslinking may occur. In some aspects, the silane-crosslinkablepolyolefin blend 212 may be about 25% cured, about 30% cured, about 35%cured, about 40% cured, about 45% cured, about 50% cured, about 55%cured, about 60% cured, bout 65% cured, or about 70% cured where geltest (ASTM D2765) can be used to determine the amount of crosslinking inthe final dense silane-crosslinked polyolefin elastomer.

Still referring to FIGS. 8 and 9B, the method 300 further includes astep 312 of molding the silane-crosslinkable polyolefin blend 212 intothe uncured combined sealing element. The single screw extruder 218melts and extrudes the silane-crosslinkable polyolefin through a diethat can extrude the molten silane-crosslinkable polyolefin blend 212into the uncured combined sealing element, for example, uncured orpartially cured versions of the combined sealing members 12, such as theprimary door seal 126, microdense sealing member 136, and others.

Referring again to FIG. 8, the method 300 can further include a step 316of crosslinking the silane-crosslinkable polyolefin blend 212 or thecombined sealing member 12 in an uncured form at an ambient temperatureand/or an ambient humidity to form the combined sealing member 12 (seeFIGS. 1 and 2) with dense portions having a density from about 0.85g/cm³ to about 0.89 g/cm³, micro-dense portions having a density fromabout 0.60 g/cm³ to about 0.69 g/cm³, and dynamic portions having adensity from about 0.50 g/cm³ to about 0.59 g/cm³. More particularly, inthis crosslinking process, the water hydrolyzes the silane of thesilane-crosslinkable polyolefin elastomer to produce a silanol. Thesilanol groups on various silane grafts can then be condensed to formintermolecular, irreversible Si—O—Si crosslink sites. The amount ofcrosslinked silane groups, and thus the final polymer properties, can beregulated by controlling the production process, including the amount ofcatalyst used.

The crosslinking/curing of step 316 of the method 300 may occur over atime period of from greater than 0 to about 20 hours. In some aspects,curing takes place over a time period of from about 1 hour to about 20hours, 10 hours to about 20 hours, from about 15 hours to about 20hours, from about 5 hours to about 15 hours, from about 1 hour to about8 hours, or from about 3 hours to about 6 hours. The temperature duringthe crosslinking/curing may be about room temperature, from about 20° C.to about 25° C., from about 20° C. to about 150° C., from about 25° C.to about 100° C., or from about 20° C. to about 75° C. The humidityduring curing may be from about 30% to about 100%, from about 40% toabout 100%, or from about 50% to about 100%.

In some aspects, an extruder setting is used that is capable ofextruding thermoplastic, with long LID, 30 to 1, at an extruder heatsetting close to TPV processing conditions wherein the extrudatecrosslinks at ambient conditions becoming a thermoset in properties. Inother aspects, this process may be accelerated by steam exposure.Immediately after extrusion, the gel content (also called the crosslinkdensity) may be about 60%, but after 96 hrs at ambient conditions, thegel content may reach greater than about 95%.

In some aspects, one or more reactive single screw extruders 218 may beused to form the uncured combined sealing element and correspondingcombined sealing member that have two or more types ofsilane-crosslinked polyolefin elastomers (i.e., dense, micro-dense anddynamic). For example, in some aspects, one reactive single screwextruder 218 may be used to produce and extrude the densesilane-crosslinked polyolefin elastomer while a second reactive singlescrew extruder 218 may be used to produce and extrude the dynamic ormicrodense silane-crosslinked polyolefin elastomer. The complexity andarchitecture of the final combined sealing member 12 will determine thenumber and types of reactive single screw extruder 218, along with thetwo or more types of silane-crosslinked polyolefin elastomers includedin the member 12.

It is understood that the description outlining and teaching the variouscombined sealing members 12, and their respective components andcompositions, can be used in any combination, and applies equally wellto the method 300 for making the combined sealing member using thetwo-step Sioplas process as shown in FIGS. 8-9B.

Referring now to FIGS. 10 and 11, a method 400 for making a combinedseal, such as combined sealing member 12, using the one-step Monosilprocess is shown. The method 400 may begin with a step 404 that includesextruding (e.g., with a single screw extruder 230) the first polyolefin170 having a density less than 0.86 g/cm³, the second polyolefin 174,the silan cocktail 178 including the silane crosslinker (e.g.,vinyltrimethoxy silane, VTMO) and grafting initiator (e.g. dicumylperoxide), and the condensation catalyst 210 together to form thecrosslinkable silane-grafted polyolefin blend. The first polyolefin 170,second polyolefin 174, and silan cocktail 178 may be added to thereactive single screw extruder 230 using an addition hopper 186. In someaspects, the silan cocktail 178 may be added to a single screw 234further down the extrusion line to help promote better mixing with thefirst and second polyolefin 170, 174 blend. In some aspects, one or moreoptional additives 214 (e.g., foaming agents for purposes of producingmicro-dense and/or dynamic silane-crosslinked polyolefin elastomers) maybe added with the first polyolefin 170, second polyolefin 174, and silancocktail 178 to tweak the final material properties of thesilane-crosslinkable polyolefin blend 212. The single screw extruder 182is considered reactive because the radical initiator and silanecrosslinker of the silan cocktail 178 are reacting with and forming newcovalent bonds with both the first and second polyolefin blends 170,174. In addition, the reactive single screw extruder 230 mixes thecondensation catalyst 210 in together with the melted silane-graftedpolyolefin blend. The melted silane-crosslinkable polyolefin blend 212can exit the reactive single screw extruder 230 using a gear pump (notshown) and/or die that can inject, eject, and/or extrude the moltensilane-crosslinkable polyolefin blend into the uncured combined sealingelement.

During step 404, as the first polyolefin 170, second polyolefin 174,silan cocktail 178, and condensation catalyst 210 are extruded together,a certain amount of crosslinking may occur in the reactive single screwextruder 230 (see FIGS. 10 and 11). In some aspects, thesilane-crosslinkable polyolefin blend 212 may be about 25% cured, about30% cured, about 35% cured, about 40% cured, about 45% cured, about 50%cured, about 55% cured, about 60% cured, bout 65% cured, or about 70% asit leaves the reactive single screw extruder 230. The gel test (ASTMD2765) can be used to determine the amount of crosslinking in the finalsilane-crosslinked polyolefin elastomer, e.g., dense, micro-dense and/ordynamic poloyolefin elastomers.

The reactive single screw extruder 230 can be configured to have aplurality of different temperature zones (e.g., Z0-Z7 as shown in FIG.11) that extend for various lengths along the extruder. In some aspects,the respective temperature zones may have temperatures ranging fromabout room temperature to about 180° C., from about 120° C. to about170° C., from about 120° C. to about 160° C., from about 120° C. toabout 150° C., from about 120° C. to about 140° C., from about 120° C.to about 130° C., from about 130° C. to about 170° C., from about 130°C. to about 160° C., from about 130° C. to about 150° C., from about130° C. to about 140° C., from about 140° C. to about 170° C., fromabout 140° C. to about 160° C., from about 140° C. to about 150° C.,from about 150° C. to about 170° C., and from about 150° C. to about160° C. In some aspects, Z0 may have a temperature from about 60° C. toabout 110° C. or no cooling; Z1 may have a temperature from about 120°C. to about 130° C.; Z2 may have a temperature from about 140° C. toabout 150° C.; Z3 may have a temperature from about 150° C. to about160° C.; Z4 may have a temperature from about 150° C. to about 160° C.;Z5 may have a temperature from about 150° C. to about 160° C.; Z6 mayhave a temperature from about 150° C. to about 160° C.; and Z7 may havea temperature from about 150° C. to about 160° C.

In some aspects, the number average molecular weight of thesilane-grafted polyolefin elastomers may be in the range of from about4,000 g/mol to about 30,000 g/mol, including from about 5,000 g/mol toabout 25,000 g/mol and from about 6,000 g/mol to about 14,000 g/mol. Theweight average molecular weight of the grafted polymers may be fromabout 8,000 g/mol to about 60,000 g/mol, including from about 10,000g/mol to about 30,000 g/mol.

Still referring to FIGS. 10 and 11, the method 400 further includes astep 408 of molding the silane-crosslinkable polyolefin blend into theuncured combined sealing element. The reactive single screw extruder 230can melt and extrude the silane-crosslinkable polyolefin through the diethat can extrude the molten silane-crosslinkable polyolefin blend intothe uncured combined sealing element to then be cured into the combinedsealing member 12 (see FIGS. 1 and 2), such as the primary door seal126, microdense sealing member 136, and others.

Still referring to FIG. 10, the method 400 can further include a step412 of crosslinking the silane-crosslinkable polyolefin blend 212 of theuncured combined sealing element at an ambient temperature and anambient humidity to form the element into the combined seal, such ascombined sealing member 12 having a density from about 0.85 g/cm³ toabout 0.89 g/cm³, for example. The amount of crosslinked silane groups,and thus the final polymer properties, can be regulated by controllingthe production process, including the amount of catalyst used.

The step 412 of crosslinking the silane-crosslinkable polyolefin blendmay occur over a time period of from greater than 0 to about 20 hours.In some aspects, curing takes place over a time period of from about 1hour to about 20 hours, 10 hours to about 20 hours, from about 15 hoursto about 20 hours, from about 5 hours to about 15 hours, from about 1hour to about 8 hours, or from about 3 hours to about 6 hours. Thetemperature during the crosslinking and curing may be about roomtemperature, from about 20° C. to about 25° C., from about 20° C. toabout 150° C., from about 25° C. to about 100° C., or from about 20° C.to about 75° C. The humidity during curing may be from about 30% toabout 100%, from about 40% to about 100%, or from about 50% to about100%.

In some aspects, an extruder setting is used that is capable ofextruding thermoplastic, with long LID, 30 to 1, at an extruder heatsetting close to TPV processing conditions wherein the extrudatecrosslinks at ambient conditions becoming a thermoset in properties. Inother aspects, this process may be accelerated by steam exposure.Immediately after extrusion, the gel content (also called the crosslinkdensity) may be about 60%, but after 96 hrs at ambient conditions, thegel content may reach greater than about 95%.

In some aspects, one or more reactive single screw extruders 230 (seeFIG. 11) may be used to form the uncured sealing element andcorresponding combined sealing member that have one or more types ofsilane-crosslinked polyolefin elastomers. For example, in some aspects,one reactive single screw extruder 230 may be used to produce andextrude a dense silane-crosslinked polyolefin elastomer while a secondreactive single screw extruder 230 may be used to produce and extrude adynamic or microdense silane-crosslinked polyolefin elastomer. Step 412can then be used to cross-link these various types of polyolefins (e.g.,in contact with one another in a mold) at the same to form a final,combined sealing element 12. As such, the complexity, architecture andtechnical specifications of the final combined sealing member 12 willdetermine the number and types of reactive single screw extruder 230.

It is understood that the description outlining and teaching the variouscombined sealing members 12, and their respective components andcompositions, can be used in any combination, and applies equally wellto the method 400 for making the combined sealing member using theone-step Monosil process as shown in FIGS. 10 and 11.

Non-limiting examples of articles incorporating combined sealing membersthat include two or more types of silane-crosslinked polyolefinelastomers of the disclosure include: seals such as weather seals (e.g.,glass run channels including molded details/corners), sunroof seals,convertible top seals, mirror seals, body-panel interface seals,stationary window moldings, glass encapsulations, cut-line seals,greenhouse moldings, occupation detector system sensor switches, rockerseals, outer and inner belts, auxiliary and margin seals, edgeprotector/gimp seals, and below-belt brackets and channels; automotivehoses such as coolant hoses, air conditioning hoses, and vacuum hoses;anti-vibration system (AVS) components such as mounts (e.g., engine,body, accessory, component), dampers, bushings, strut mounts, andisolators; coatings such as coatings for brake lines, fuel lines,transmission oil cooler lines, brackets, cross members, framecomponents, body panels and components, suspension components, wheels,hubs, springs, and fasteners; air deflectors, spoilers, fascia, andtrim; building, window, and door seals; boots, bellows, and grommets;gaskets (e.g., pneumatic and/or hydraulic gaskets); wire and cablesheathing; tires; windshield wipers and squeegees; floor mats; pedalcovers; automotive belts; conveyor belts; shoe components; marinebumpers; O-rings; valves and seals; and springs (e.g., as substitutesfor mechanical metal springs).

Dense, Dynamic and Micro-dense Silane-Crosslinked Polyolefin ElastomerPhysical Properties

A “thermoplastic”, as used herein, is defined to mean a polymer thatsoftens when exposed to heat and returns to its original condition whencooled to room temperature. A “thermoset”, as used herein, is defined tomean a polymer that solidifies and irreversibly “sets” or “crosslinks”when cured. In either of the Monosil or Sioplas processes describedabove, it is important to understand the careful balance ofthermoplastic and thermoset properties of the various differentmaterials used to produce the final thermoset dense, dynamic andmicro-dense silane-crosslinked polyolefin elastomers, as employed in thecombined sealing members. Each of the intermediate polymer materialsmixed and reacted using a reactive twin screw extruder, a reactivesingle screw extruder, and/or a reactive single screw extruder arethermosets. Accordingly, the silane-grafted polyolefin blend and thesilane-crosslinkable polyolefin blend are thermoplastics and can besoftened by heating so the respective materials can flow. Once thesilane-crosslinkable polyolefin blend is extruded, molded, pressed,and/or shaped into the uncured sealing element or other respectivearticle, the silane-crosslinkable polyolefin blend can begin tocrosslink or cure at an ambient temperature and an ambient humidity toform the combined sealing member as comprising two or more of the dense,dynamic and micro-dense, silane-crosslinked polyolefin blends.

The thermoplastic/thermoset behavior of the silane-crosslinkablepolyolefin blend and corresponding dense, dynamic and micro-densesilane-crosslinked polyolefin blends are important for the variouscompositions and articles disclosed herein (e.g., combined sealingmembers 12 shown in FIGS. 1 and 2) because of the potential energysavings provided using these materials. For example, a manufacturer cansave considerable amounts of energy by being able to cure thesilane-crosslinkable polyolefin blend at an ambient temperature and anambient humidity. This curing process is typically performed in theindustry by applying significant amounts of energy to heat or steamtreat crosslinkable polyolefins. The ability to cure the inventivesilane-crosslinkable polyolefin blend with ambient temperature and/orambient humidity are not properties necessarily intrinsic tocrosslinkable polyolefins, but rather is a property dependent on therelatively low density (i.e., as compared to EPDM and/or TPV) of thesilane-crosslinkable polyolefin blend. In some aspects, no additionalcuring overs, heating ovens, steam ovens, or other forms of heatproducing machinery other than what was provided in the extruders areused to form the dense, dynamic and micro-dense silane-crosslinkedpolyolefin elastomers.

The specific gravity of the dense silane-crosslinked polyolefinelastomers of the present disclosure may be lower than the specificgravities of existing TPV and EPDM formulations used in the art. Thereduced specific gravity of these materials can lead to lower weightparts, thereby helping automakers meet increasing demands for improvedfuel economy. For example, the specific gravity of the densesilane-crosslinked polyolefin elastomer of the present disclosure may befrom about 0.80 g/cm³to about 0.89 g/cm³, from about 0.85 g/cm³to about0.89 g/cm³, less than 0.90 g/cm³, less than 0.89 g/cm³, less than 0.88g/cm³, less than 0.87 g/cm³, less than 0.86 g/cm³, or less than 0.85g/cm³ as compared to existing TPV materials which may have a specificgravity of from 0.95 to 1.2 g/cm³ and EPDM materials which may have aspecific gravity of from 1.0 to 1.35 g/cm³. The low specific gravity ordensity of the dense silane-crosslinked polyolefin elastomer isattributable to the low crystallinity of the elastomers found inExamples 1-7 described below. In some aspects, the percent crystallinityof the dense silane-crosslinked polyolefin elastomer is less than 10%,less than 20%, or less than 30%.

With regard to the dynamic silane-crosslinked polyolefin elastomers ofthe disclosure, the specific gravity of these elastomers may also belower than the specific gravities of existing TPV and EPDM formulationsused in the art. The reduced specific gravity of these materials canlead to lower weight parts, thereby helping automakers meet increasingdemands for improved fuel economy. For example, the specific gravity ofthe dynamic silane-crosslinked polyolefin elastomer of the presentdisclosure may be from about 0.40 g/cm³to about 0.59 g/cm³, from about0.50 g/cm³to about 0.59 g/cm³, from about 0.40 g/cm³to about 0.49 g/cm³,less than 0.60 g/cm³, less than 0.55 g/cm³, less than 0.50 g/cm³, orless than 0.45 g/cm³ as compared to existing TPV materials which mayhave a specific gravity of from 0.95 to 1.2 g/cm³ and EPDM materialswhich may have a specific gravity of from 1.0 to 1.35 g/cm³. The lowspecific gravity or density of the dynamic silane-crosslinked polyolefinelastomer is attributable to the low crystallinity of the found in theExamples described below. In some aspects, the percent crystallinity ofthe dynamic silane-crosslinked polyolefin elastomer is less than 10%,less than 20%, or less than 30%.

The specific gravity of the microdense silane-crosslinked polyolefinelastomer of the present disclosure may be lower than the specificgravities of conventional TPV- and EPDM-based formulations used in theart. The reduced specific gravity of these materials can lead to lowerweight parts, thereby helping automakers meet increasing demands forimproved fuel economy. For example, the specific gravity of themicrodense silane-crosslinked polyolefin elastomer of the presentdisclosure may be from about 0.40 g/cm³to about 0.59 g/cm³, from about0.50 g/cm³to about 0.59 g/cm³, from about 0.40 g/cm³to about 0.49 g/cm³,less than 0.60 g/cm³, less than 0.55 g/cm³, less than 0.50 g/cm³, orless than 0.45 g/cm³ as compared to existing TPV materials which mayhave a specific gravity of from 0.95 to 1.2 g/cm³ and EPDM materialswhich may have a specific gravity of from 1.0 to 1.35 g/cm³. The lowspecific gravity or density of the foamed (microdense)silane-crosslinked polyolefin elastomer is attributable to the lowcrystallinity of the polyolefin elastomers found in the Examplesdescribed below. In some aspects, the percent crystallinity of thefoamed silane-crosslinked polyolefin elastomer is less than 10%, lessthan 20%, or less than 30%.

Referring now to FIG. 12, the stress/strain behavior of an exemplarysilane-crosslinked polyolefin elastomer of the present disclosure (i.e.,the “Silane-Crosslinked Polyolefin Elastomer” in the legend) relative totwo existing, comparative EPDM materials is provided. In particular,FIG. 12 displays a smaller area between the stress/strain curves for thesilane-crosslinked polyolefin of the disclosure, versus the areasbetween the stress/strain curves for EPDM compound A and EPDM compoundB. This smaller area between the stress/strain curves for thesilane-crosslinked polyolefin elastomer can be desirable for seals andweatherstrips used with automotive glass applications. Elastomericmaterials typically have non-linear stress-strain curves with asignificant loss of energy when repeatedly stressed. Thesilane-crosslinked polyolefin elastomers of the present disclosure mayexhibit greater elasticity and less viscoelasticity (e.g., have linearcurves and exhibit very low energy loss). Embodiments of thesilane-crosslinked polyolefin elastomers described herein do not haveany filler or plasticizer incorporated into these materials so theircorresponding stress/strain curves do not have or display any Mullinseffect and/or Payne effect. The lack of Mullins effect for thesesilane-crosslinked polyolefin elastomers is due to the lack of anyconventional reinforcing fillers (e.g., carbon black) or plasticizeradded to the silane-crosslinked polyolefin blend so the stress-straincurve does not depend on the maximum loading previously encounteredwhere there is no instantaneous and irreversible softening. The lack ofPayne effect for these silane-crosslinked polyolefin elastomers is dueto the lack of any filler or plasticizer added to the silane-crosslinkedpolyolefin blend so the stress-strain curve does not depend on the smallstrain amplitudes previously encountered where there is no change in theviscoelastic storage modulus based on the amplitude of the strain.

The silane-crosslinked polyolefin elastomers employed in the combinedsealing members of the disclosure can exhibit a compression set of fromabout 5.0% to about 30.0%, from about 5.0% to about 25.0%, from about5.0% to about 20.0%, from about 5.0% to about 15.0%, from about 5.0% toabout 10.0%, from about 10.0% to about 25.0%, from about 10.0% to about20.0%, from about 10.0% to about 15.0%, from about 15.0% to about 30.0%,from about 15.0% to about 25.0%, from about 15.0% to about 20.0%, fromabout 20.0% to about 30.0%, or from about 20.0% to about 25.0%, asmeasured according to ASTM D 395 (22 hrs @ 23° C., 70° C., 80° C., 90°C., 125° C., and/or 175° C.).

In other implementations, the silane-crosslinked polyolefin elastomer ofthe combined sealing members can exhibit a compression set of from about5.0% to about 20.0%, from about 5.0% to about 15.0%, from about 5.0% toabout 10.0%, from about 7.0% to about 20.0% , from about 7.0% to about15.0%, from about 7.0% to about 10.0%, from about 9.0% to about 20.0%,from about 9.0% to about 15.0%, from about 9.0% to about 10.0%, fromabout 10.0% to about 20.0%, from about 10.0% to about 15.0%, from about12.0% to about 20.0%, or from about 12.0% to about 15.0%, as measuredaccording to ASTM D 395 (22 hrs @ 23° C., 70° C., 80° C., 90° C., 125°C., and/or 175° C.).

The silane-crosslinked polyolefin elastomers of the combined sealingmembers of the disclosure may exhibit a crystallinity of from about 5%to about 40%, from about 5% to about 25%, from about 5% to about 15%,from about 10% to about 20%, from about 10% to about 15%, or from about11% to about 14% as determined using density measurements, differentialscanning calorimetry (DSC), X-Ray Diffraction, infrared spectroscopy,and/or solid state nuclear magnetic spectroscopy. As disclosed herein,DSC was used to measure the enthalpy of melting in order to calculatethe crystallinity of the respective samples.

The silane-crosslinked polyolefin elastomers of the combined sealingmembers of the disclosure may exhibit a glass transition temperature offrom about −75° C. to about −25° C., from about −65° C. to about −40°C., from about −60° C. to about −50° C., from about −50° C. to about−25° C., from about −50° C. to about −30° C., or from about −45° C. toabout −25° C. as measured according to differential scanning calorimetry(DSC) using a second heating run at a rate of 5° C./min or 10° C./min.

The silane-crosslinked polyolefin elastomers of the combined sealingmembers of the disclosure may exhibit a weathering color difference offrom about 0.25 ΔE to about 2.0 ΔE, from about 0.25 ΔE to about 1.5 ΔE,from about 0.25 ΔE to about 1.0 ΔE, or from about 0.25 ΔE to about 0.5ΔE, as measured according to ASTM D2244 after 3000 hrs exposure toexterior weathering conditions.

The silane-crosslinked polyolefin elastomers of the combined sealingmembers of the disclosure may exhibit exceptional stain resistanceproperties as compared to EPDM samples. Ex. 3, as disclosed below,showed no cracking, wrinkling, crazing, iridescence, bloom, milkiness,separation, loss of adhesion, or loss of embossment as measuredaccording to ASTM D1566. In addition, Ex. 3 which is representative ofall the silane-crosslinked polyolefin elastomers produced, showed nospotting or discoloration in pH 11, pH 12.5, and pH 13 NaOH solutions asmeasured according to SunSimulation and Spotting Test (PR231-2.2.15).

EXAMPLES

The following examples represent certain non-limiting examples of thecompositions of the combined sealing members, and methods of makingthem, according to the disclosure.

Materials

All chemicals, precursors and other constituents were obtained fromcommercial suppliers and used as provided without further purification.

As detailed below, Examples 1-7 relate to dense silane-crosslinkedpolyolefin elastomers of the disclosure, Examples [TBD]

Example 1

Example 1 or ED4 was produced by extruding 77.36 wt % ENGAGE 8150 and19.34 wt % VISTAMAX 6102 together with 3.3 wt % SILFIN 13 to form thesilane-grafted polyolefin elastomer. The Example 1 silane-graftedpolyolefin elastomer was then extruded with 3 wt % Ambicat LE4472condensation catalyst to form a silane-crosslinkable polyolefinelastomer, which was then extruded into an uncured sealing member. TheExample 1 silane-crosslinkable polyolefin elastomer of the uncuredsealing member was cured at ambient temperature and humidity to form asilane-crosslinked polyolefins elastomer, consistent with the densesilane-crosslinked polyolefin elastomers of the disclosure. Thecomposition of Example 1 is provided in Table 1 below.

Example 2

Example 2 or ED76-4A was produced by extruding 82.55 wt % ENGAGE 8842and 14.45 wt % MOSTEN TB 003 together with 3.0 wt % SILAN RHS 14/032 orSILFIN 29 to form the silane-grafted polyolefin elastomer. The Example 2silane-grafted polyolefin elastomer was then extruded with 3 wt %Ambicat LE4472 condensation catalyst to form a silane-crosslinkablepolyolefin elastomer, which was then extruded into an uncured sealingmember. The Example 2 silane-crosslinkable polyolefin elastomer of theuncured sealing member was cured at ambient temperature and humidity toform a silane-crosslinked polyolefins elastomer, consistent with thedense silane-crosslinked polyolefin elastomers of the disclosure. Thecomposition of Example 2 is provided in Table 1 below and some of itsmaterial properties are provided in FIGS. 13-19.

Example 3

Example 3 or ED76-4E was produced by extruding 19.00 wt % ENGAGE 8150,58.00 wt %

ENGAGE 8842, and 20.00 wt % MOSTEN TB 003 together with 3.0 wt % SILANRHS 14/032 or SILFIN 29 to form the silane-grafted polyolefin elastomer.The Example 3 silane-grafted polyolefin elastomer was then extruded with3 wt % Ambicat LE4472 condensation catalyst to form thesilane-crosslinkable polyolefin elastomer, which was then extruded intoan uncured sealing member. The Example 3 silane-crosslinkable polyolefinelastomer of the uncured sealing member was cured at ambient temperatureand humidity to form a silane-crosslinked polyolefin elastomer,consistent with the dense silane-crosslinked polyolefin elastomers ofthe disclosure. The composition of Example 3 is provided in Table 1below.

Example 4

Example 4 or ED76-5 was produced by extruding 19.00 wt % ENGAGE 8150,53.00 wt % ENGAGE 8842, and 25.00 wt % MOSTEN TB 003 together with 3.0wt % SILAN RHS 14/032 or SILFIN 29 to form the silane-grafted polyolefinelastomer. The Example 4 silane-grafted polyolefin elastomer was thenextruded with 3 wt % Ambicat LE4472 condensation catalyst to form thesilane-crosslinkable polyolefin elastomer, which was then extruded intoan uncured sealing member. The Example 4 silane-crosslinkable polyolefinelastomer of the uncured sealing member was cured at ambient temperatureand humidity to form a silane-crosslinked polyolefins elastomer,consistent with the dense silane-crosslinked polyolefin elastomers ofthe disclosure. The composition of Example 4 is provided in Table 1below.

Example 5

Example 5 or ED76-6 was produced by extruding 16.36 wt % ENGAGE 8150,45.64 wt % ENGAGE 8842, and 35.00 wt % MOSTEN TB 003 together with 3.0wt % SILAN RHS 14/032 or SILFIN 29 to form the silane-grafted polyolefinelastomer. The Example 5 silane-grafted polyolefin elastomer was thenextruded with 3 wt % Ambicat LE4472 condensation catalyst to form thesilane-crosslinkable polyolefin elastomer, which was then extruded intoan uncured sealing member. The Example 5 silane-crosslinkable polyolefinelastomer of the uncured sealing member was cured at ambient temperatureand humidity to form a silane-crosslinked polyolefins elastomer,consistent with the dense silane-crosslinked polyolefin elastomers ofthe disclosure. The composition of Example 5 is provided in Table 1below.

Table 1 below sets forth the compositions of the dense silane-graftedpolyolefin elastomers of Examples 1-5.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 ENGAGE 8150 77.36 — 19.00 19.0016.36 ENGAGE 8842 — 82.55 58.00 53.00 45.64 MOSTEN TB 003 — 14.45 20.0025.00 35.00 VISTAMAXX 6102 19.34 — — — — SILAN RHS 14/032 — 3.00 3.003.00 3.00 or SILFIN 29 SILFIN 13 3.30 — — — — TOTAL 100 100 100 100 100

Example 6

Example 6 or ED108-2A was produced by extruding 48.7 wt % ENGAGE XLT8677or XUS 38677.15 and 48.7 wt % ENGAGE 8842 together with 2.6 wt % SILANRHS 14/032 or SILFIN 29 to form the silane-grafted polyolefin elastomer.The Example 6 silane-grafted polyolefin elastomer was then extruded withabout 360 ppm dioctyltin dilaurate (DOTL) condensation catalyst to forma silane-crosslinkable polyolefin elastomer as an uncured sealingmember. The Example 6 silane-crosslinkable polyolefin elastomer of theuncured sealing member was cured at ambient temperature and humidity toform a silane-crosslinked polyolefins elastomer, consistent with thedense silane-crosslinked polyolefin elastomers of the disclosure. Thecomposition of Example 6 is provided in Table 2 below and some of itsmaterial properties are provided in FIGS. 13-19.

Example 7

Example 7 or ED92 was produced by extruding 41.4 wt % ENGAGE XLT8677 orXUS 38677.15 and 41.4 wt % ENGAGE 8842, and 14.4 wt % MOSTEN TB 003together with 2.8 wt % SILAN RHS 14/032 or SILFIN 29 to form thesilane-grafted polyolefin elastomer. The Example 7 silane-graftedpolyolefin elastomer was then extruded with about 360 ppm dioctyltindilaurate (DOTL) condensation catalyst to form a silane-crosslinkablepolyolefin elastomer as an uncured sealing member. The Example 7silane-crosslinkable polyolefin elastomer of the uncured sealing memberwas cured at ambient temperature and humidity to form asilane-crosslinked polyolefins elastomer, consistent with the densesilane-crosslinked polyolefin elastomers of the disclosure. Thecomposition of Example 7 is provided in Table 2 below and some of itsmaterial properties are provided in FIGS. 13-19.

Table 2 below sets forth the compositions of the dense silane-graftedpolyolefin elastomers of Examples 6-7.

TABLE 2 Ingredients Ex. 6 Ex. 7 ENGAGE XLT8677/XUS 38677.15 48.7 41.4ENGAGE 8842 48.7 41.4 SILAN RHS 14/032 or SILFIN 29 2.6 2.8 MOSTEN TB003 — 14.4 TOTAL 100 100

Table 3 below sets forth several of the material properties ofExample 1. In particular, plied compression set percentages are providedusing ASTM D 395, method B for 22 hrs at 23° C., 70° C., 80° C., 90° C.,125° C., and 175° C. Example 1 is representative of the densesilane-crosslinked polyolefin elastomers disclosed herein in that thecompression set percentage does not vary as much as standard EPDM or TPVmaterials do across a range of different temperatures. In some aspects,the percent difference in plied compression set percentage values forthe dense silane-crosslinked polyolefin elastomer is less than 400%,less than 300%, less than 275%, less than 250%, less than 225%, or lessthan 210%.

TABLE 3 Test Ex. 1 Durometer (Type A per ASTM D 2240) 75 Tensile MPa(ASTM D 412, die C) 9.8 Elongation % (ASTM D 412, die C) 291 TearResistance (ASTM D624, die C) 19 22 hrs/23° C. Plied Compression Set %20.0 22 hrs/70° C. Plied Compression Set % 12.6 22 hrs/80° C. PliedCompression Set 16.5 22 hrs/90° C. Plied Compression Set % 10.9 22hrs/125° C. Plied Compression Set % 7.6 22 hrs/175° C. Plied CompressionSet % 9.6 Gel % 90

Table 4 below sets forth density, hardness, low and high temperatureperformance, compression set, and weathering material properties forExamples 2-4.

TABLE 4 Property Test Method Units/Output Ex. 2 Ex. 3 Ex. 4 OriginalsDensity ASTM D297 g/cc 0.88 0.89 0.89 Hardness ASTM D412 Shore A 76 8488 Die C Tensile ASTM D412 MPa 10.4 13.2 14.5 Die C Elongation ASTM D412% 300 306 314 Die C Tear C ASTM D624 N/mm 24 37 48 Die C Hardness JIS K6253 IRHD 72 82 87 Tensile JIS K 6251 MPa 8.3 13.3 16.1 Elongation JIS K6251 % 260 255 334 Tear C JIS K 6252 N/cm 249 401 564 Low & HighHardness Heat Age (70 h/100° C.) ASTM D573 Change −2 −2 1 Temperature(Shore A) Performance Tensile Heat Age (70 h/100° C.) ASTM D573 % Change−3.1 −6 9.1 Elongation Heat Age (70 h/100° C.) ASTM D573 % Change −10.4−8.7 −2.6 Hardness Heat Age (168 h/100° C.) JIS K 6251/7 Change 0 2 −5(IRHD) Tensile Heat Age (168 h/100° C.) JIS K 6251/7 % Change 0 −15.1−9.9 Elongation Heat Age (168 h/100° C.) JIS K 6251/7 % Change −18 −22.7−21 Tear Heat Age (168 h/100° C.) JIS K 6251/7 % Change −11.2 −8.7 −10Tensile Heat Age (1000 h/125° C.) ASTM D573 Change −2 −1 0 (Shore A)Elongation Heat Age ASTM D573 % Change −4.4 18.7 1.4 (1000 h/125° C.)Tear Heat Age (1000 h/125° C.) ASTM D573 % Change −6.1 −11 −8.8 −40° C.Tensile ASTM D412 % Change 38.5 — — Die C −40° C. Elongation ASTM D412 %Change 17.6 — — Die C Low Temperature (−40° C.) ASTM D2137 — NonbrittleNonbrittle Nonbrittle Method A 80° C. Tensile ASTM D412 % Change −10.8 —— Die C 80° C. Elongation ASTM D412 % Change −1.5 — — Die C CompressionPlied C/S (22 h/70° C.) ASTM D395 % 20.7 25 30 Set Method B Plied C/S(22 h/80° C.) ASTM D395 % 20.2 30.5 — Method B Plied C/S (72 h/80° C.)ASTM D395 % 22.5 32.6 — Method B Plied C/S (100 h/80° C.) ASTM D395 %39.2 44.3 54.7 Method B Plied C/S (168 h/80° C.) ASTM D395 % 29 39 —Method B Plied C/S (500 h/80° C.) ASTM D395 % 41.2 53.8 — Method B PliedC/S (1000 h/80° C.) ASTM D395 % 43.8 55.4 — Method B Plied C/S (22 h/90°C.) ASTM D395 % 22.5 32.8 — Method B Plied C/S (22 h/100° C.) ASTM D395% 25.4 35 42.5 Method B Plied C/S (70 h/125° C.) ASTM D395 % 29 37.946.6 Method B Plied C/S (22 h/135° C.) ASTM D395 % 38.5 46.6 — Method BPlied C/S (22 h/150° C.) ASTM D395 % 44.3 61 — Method B Plied C/S (22h/175° C.) ASTM D395 % 23.3 38.1 — Method B Permanent CompressiveDistortion JIS K 6257 % 30 41 43 (22 h/100° C.) Miscellaneous VolumeResistivity IEC 60093 Ω cm 2.1 × 10¹⁶ 2.2 × 10¹⁶ 2.2 × 10¹⁶ Weathering(3000 hrs.) SAE J2527 AATCC 4-5 4-5 4-5 Arizona Natural Weathering (2yrs.) SAE J1976, ΔE 1.6 1.2 1.7 Procedure A Florida Natural Weathering(2 yrs.) SAE J1976, ΔE 1.6 1.0 1.2 Procedure A Fogging SAE J1756 % 97 9697 Ozone Resistance ASTM D1171 Retention 100 100 100 Method B Rating (%)Flammability ISO 3795 Burn Rate 19 22 17 (mm/min) Odor SAE J1351 No PassPass Pass Disagreeable Odor Wet or Dry Paint Staining (24 h/70° C.) ASTMD925 — No No No Method A Staining Staining Staining

Table 5 below sets forth the chemical resistance material properties forExample 2, which is representative of all of the disclosed densesilane-crosslinked polyolefin elastomers. Method B (see Table 5)includes reporting any evidence of softening, staining, blistering,flaking, chipping, checking, chalking, cracks, spills, sinks, bulges,tackiness, peeling, or delamination. The fairness grade is 5 for a CELABdifference of 0 and a Tolerance of 0.2 and the fairness grade is 4 for aCELAB difference of 1.7 and a Tolerance of ±0.3.

TABLE 5 Test Chemical Method Units/Output Ex. 2 Solvent Resistance 7:3(Kerosene:Mineral Spirits) TSM1720G % Change in 170 (72 h/RT) VolumeFluid Resistance Gasoline 87 Octane, Lead Free, 20% FLTM BI 168-01,Rating (see Pass, 4 Ethanol Method B above) Diesel, Grade 2, 20%Biodiesel FLTM BI 168-01, Rating (see Pass, 4 Method B above) Coolant,Ethylene glycol/Water 50/50 FLTM BI 168-01, Rating (see Pass, 5 Method Babove) Engine Oil, Meets API-ILSAC Requirements FLTM BI 168-01, Rating(see Pass, 5 Method B above) Deionized Water FLTM BI 168-01, Rating (seePass, 5 Method B above) Multipurpose Cleaner (Formula 409, FLTM BI168-01, Rating (see Pass, 5 Fantastic, or Armor All) Method B above)Windshield Wash Fluid, Methanol Based, 1 FLTM BI 168-01, Rating (seePass, 5 Part Motorcraft Fluid to 1.5 Parts Water Method B above)Motorcraft Bug and Tar Remover FLTM BI 168-01, Rating (see Pass, 5Method B above) Glass Cleaner FLTM BI 168-01, Rating (see Pass, 5 MethodB above) Isopropyl Alcohol 1:1 with Water FLTM BI 168-01, Rating (seePass, 5 Method B above)

Referring now to FIG. 13, the compression set percentage is given byC₈=[(H₀−H₀′)/(H₀−H_(comp))×100% where H₀ is the original specimenthickness before compression, Ho is the specimen thickness aftertesting, and H_(comp) is the specimen thickness during the test. Asprovided in FIG. 13, each of Examples 2, 6, and 7 (“Exs. 2, 6 and 7” inFIG. 13) made from the dense silane-crosslinked polyolefin elastomersexhibited a lower compression set after one hour and a higher speed ofset recovery as compared to TOSE 539 70 (“TPS” in FIG. 13), a styrenicTPV or TPS, and SANTOPRENE 12167W175 (“EPDM/PP” in FIG. 13), a EPDM/PPcopolymer. The compression set percentages provided by each of the densesilane-crosslinked polyolefin elastomers (Exs. 2, 6 and 7) relative tothe comparative TPV and EPDM materials demonstrate the improved highelastic properties exhibited by these materials.

Referring now to FIG. 14, the lip set recovery percentage is given byLSR=[(L₀′)/(L₀)×100% where L₀ is the original lip thickness beforecompression and L₀′ is the lip thickness after testing. As provided inFIG. 14, each of Examples 2, 6, and 7 made from the densesilane-crosslinked polyolefin elastomers exhibited a higher lip setrecovery after one hour (97%, 97.5%, and 99.2%, respectively) and ahigher speed of lip set recovery as compared to TPS (93%) or EPDM/PPcopolymer (94%). Again, the lip set recovery percentages provided byeach of the dense silane-crosslinked polyolefin elastomers relative toTPV and EPDM materials demonstrate the improved elastic propertiesexhibited by these materials.

Referring now to FIG. 15, the lip relaxation rate percentage for 1 hr at23° C. is given by R(%)=(F₀−F_(t))/(F₀) where F₀ is the initial forcerequired for the first compression and F_(t) is the final force requiredfor compression for the testing period. As provided in FIG. 15, each ofExamples 2, 6, and 7 made from the dense silane-crosslinked polyolefinelastomers exhibited an improved relaxation rate as compared to TPS orEPDM/PP copolymer.

Referring now to FIG. 16, the stress/strain behavior of an exemplarydense silane-crosslinked polyolefin elastomer of the present disclosureis provided. The traces in FIG. 16 demonstrate the particularly smallareas that can be achieved between the stress/strain curves for thesilane-crosslinked polyolefin of the disclosure. Elastomeric materialstypically have non-linear stress-strain curves with a significant lossof energy when repeatedly stressed. The silane-crosslinked polyolefinelastomers of the present disclosure exhibit greater elasticity and lessviscoelasticity (e.g., have linear curves and exhibit very low energyloss). The lack of any filler or plasticizer in these materials lead tono demonstration of any Mullins and/or Payne effect.

Referring now to FIG. 17, compression set performance is provided acrossa range of elevated temperatures and increasing periods of time forExample 1 (“Ex. 1” in FIG. 17), a comparative TPV material (“TPV” inFIG. 17), and a comparative EPDM material (“EPDM” in FIG. 17). As shownin the graph, the compression set % of the dense silane-crosslinkedpolyolefin elastomer (Ex. 1) increases slightly over the providedincreasing temperatures (70° C.-175° C.) and test times (22 h-1000 h)relative to the comparative TPV and EPDM materials.

Referring now to FIG. 18, compression set performance is provided acrossa range of elevated temperatures and increasing periods of time forExample 1, a comparative TPV material, and a comparative EPDM material.As shown in the graph, the compression set % of the densesilane-crosslinked polyolefin elastomer (Ex. 1) increases slightly overthe provided increasing temperatures (23° C.-175° C.) for a test time of22 h relative to the comparative TPV and EPDM materials. The compressionset % of the Ex. 1 dense silane-crosslinked polyolefin elastomer stayssurprisingly even across the provided temperature range as compared tothe dramatic increase in compression set % demonstrated for the TPV andEPDM materials.

FIG. 19 and Table 6 below provide additional data regarding thecompression set performance of Examples 2-4 relative to EPDM 9724 andTPV 121-67. Table 6 provides compression set data performed intriplicate for Examples 2-4 relative to EPDM 9724 (“EPDM”) and TPV121-67 (“TPV”). FIG. 19 plots the average compression set values forthese samples performed at 72 hrs at 23° C. and 70 hrs at 125° C.

TABLE 6 Compound 72 h/23° C. 70 h/125° C. Ex. 2 13.8 22.1 Ex. 2 15.722.3 Ex. 2 20.4 22.9 Avg. 16.6 22.4 Ex. 3 19.9 31.0 Ex. 3 21.4 33.6 Ex.3 23.6 33.6 Avg. 21.6 32.7 Ex. 4 24.8 41.9 Ex. 4 24.6 40.2 Ex. 4 28.440.0 Avg. 25.9 40.7 EPDM 5.6 75.4 EPDM 8.3 76.3 EPDM 11.5 82.3 Avg. 8.578.0 TPV 21.2 51.2 TPV 21.4 52.4 TPV 21.5 47.8 Avg. 21.4 50.5

Example 8

Example 8 (Ex. 8) or ED108-2A was produced by extruding 48.70 wt %ENGAGE 8842 and 48.70 wt % XUS38677.15 together with 2.6 wt % SI LAN RHS14/032 or SILFIN 13 to form a silane-grafted polyolefin elastomer. TheExample 8 silane-grafted polyolefin elastomer was then extruded with 1.7wt % Hydrocerol 1170 foaming agent, 2 wt % Ambicat LE4472 condensationcatalyst, and 360 ppm dioctyltin dilaurate (DOTL) condensation catalystto form a silane-crosslinkable polyolefin elastomer, which was thenextruded into an uncured sealing member. The Example 8silane-crosslinkable polyolefin elastomer of the uncured sealing memberwas then cured at ambient temperature and humidity to form a dynamicsilane-crosslinked polyolefin elastomer, consistent with the elastomersof the disclosure. The composition of Example 8 is provided in Table 7below and its material properties are provided in Table 8 below.

Example 9

Example 9 (Ex. 9) or ED108-2B was produced by extruding 48.70 wt %ENGAGE 8842 and 48.70 wt % XUS38677.15 and 2.6 wt % SILAN RHS 14/032 orSILFIN 13 together with Exact 9061/SpectraSyn 10 (70/30) to form thesilane-grafted polyolefin elastomer. The Example 9 silane-graftedpolyolefin elastomer was then extruded with 1.7 wt % Hydrocerol 1170foaming agent, 2 wt % Ambicat LE4472 condensation catalyst, and 360 ppmdioctyltin dilaurate (DOTL) condensation catalyst to form asilane-crosslinkable polyolefin elastomer, which was then extruded intoan uncured sealing member. The Example 9 silane-crosslinkable polyolefinelastomer of the uncured sealing member was then cured at ambienttemperature and humidity to form a dynamic silane-crosslinked polyolefinelastomer, consistent with the elastomers of the disclosure. Thecomposition of Example 9 is provided in Table 7 below and its materialproperties are provided in Table 8 below. Also provided below in Table 7are properties associated with a comparative EPDM material (“EPDM”).

TABLE 7 Ingredients Ex. 8 Ex. 9 ENGAGE XLT8677/XUS 38677.15 48.7 46.25ENGAGE 8842 48.7 46.25 SILAN RHS 14/032 or SILFIN 29 2.6 2.5 Exact9061/SpectraSyn 10 (70/30) — 5 TOTAL 100 100

TABLE 8 Property Test Method Units/Output Ex. 1 Ex. 2 EPDM StructuralDensity ASTM D297 g/cc 0.52 0.55 0.66 Tensile ASTM D412 MPa 2.6 2.0 2.9Die C Elongation ASTM D412 % 230 209 354 Die C 100% Modulus ASTM D412MPa 1.5 1.4 0.80 Die C Tear C ASTM D624 N/mm 8.0 9.6 8.8 Die CCompression Plied C/S (22 h/80° C.) ASTM D395 % 29.4 35.4 47.4 Set (50%Method B compression) Plied C/S (96 h/80° C.) ASTM D395 % 37.6 58.9 56.4Method B Plied C/S (168 h/80° C.) ASTM D395 % 67.0 69.6 67.8 Method BPlied C/S (500 h/80° C.) ASTM D395 % 76.4 — 73.5 Method B Plied C/S(1000 h/80° C.) ASTM D395 % 78.6 — 97.3 Method B Miscellaneous WaterAbsorption GM9888P % 0.16 — 0.21

Referring now to FIG. 20, a load vs. position plot is provided for theEx. 8 ED108-2A resin (i.e., as prepared above in Example 8), ascrosslinked with 2% catalyst (“Ex. 8 with 2% cat”), 3% catalyst (Ex. 8with 3% cat“), and 2% catalyst with a slip coat (”Ex. 8 with 2% cat andslip coat“). A comparative example load v. position plot is provided fora traditional EPDM sponge material (”EPDM″). The Ex. 8 materials (i.e.,dynamic silane-crosslinked polyolefin elastomers according to thedisclosure) display a smaller area between the load/position curves ascompared to the areas between the load/position curves for thecomparative EPDM compound. This smaller area between the load/positioncurves for the dynamic silane-crosslinked polyolefin elastomers can bedesirable for combined sealing members, e.g., weatherstrips, that can beused for various sealing applications. Further, the Ex. 8 polyolefinblends do not contain any filler or plasticizer incorporated so each ofcorresponding load/position curves for these blends do not have ordisplay any Mullins effect and/or Payne effect.

The selection of the condensation catalyst may have an influence on thefinal material properties for a sample. For example, the Example 9ED108-2B silane-grafted polyolefin elastomer was produced by extruding48.70 wt % ENGAGE 8842 and 48.70 wt % XUS38677.15 and 2.6 wt % SILAN RHS14/032 or SILFIN 13 together with Exact 9061/SpectraSyn 10 (70/30) toform the silane-grafted polyolefin elastomer. These Example 9silane-grafted polyolefin elastomers were then extruded with twodifferent condensation catalysts: (a) with 1.7 wt % Hydrocerol 1170foaming agent, 2 wt % Ambicat LE4472 condensation catalyst, and 360 ppmdioctyltin dilaurate (DOTL) condensation catalyst; and (b) with 1.7 wt %Hydrocerol 1170 foaming agent, 2 wt % Ambicat LE4472 condensationcatalyst, and 360 ppm dibutyltin dilaurate (DBTDL) condensationcatalyst. Accordingly, two dynamic silane-crosslinkable polyolefinelastomers were formed (identified as “DOTL” and “DBTDL”), which werethen extruded into an uncured sealing member. The difference in materialproperties of these crosslinkable elastomers are given below in Tables 9and 10.

TABLE 9 Elastomer 22 h/80 C. 96 h/80 C. 168 h/80 C. Group Tube C/S (%)Tube C/S (%) Tube C/S (%) DOTL 38.9 42.1 52.3 DBTDL 25.9 27.9 34.0

TABLE 10 100% Auburn Tensile Elongation Modulus Density TC Group DuroMPa (%) (Mpa) (g/cc) (N/mm) DOTL 43 2.8 294 1.3 0.52 9.3 DBTDL 39 2.9170 1.9 0.51 7.6

Referring now to FIG. 21, cross-sectional views are provided for adynamic silane-crosslinked polyolefin elastomer, as foamed usingsupercritical gas injection and chemical foaming agents. As provided bythe images, the pore size resulting from the chemical foaming agent isfrom 20 μm to 147 μm while the pore size resulting from thesupercritical gas injection is from 46 μm to 274 μm. Depending on thetype of foaming agent selected to foam each of the respectivesilane-crosslinkable polyolefin elastomer disclosed herein, a variety ofdifferent pore sizes can be obtained which will affect the final densityof the foamed (dynamic) silane-crosslinked polyolefin elastomer. In someaspects, the pore size may be from 20 μm to 200 μm, from 25 μm to 400μm, or from 25 μm to 300 μm.

Example 10

Example 10 (Ex. 10) or ED76-4A was produced by extruding 82.55 wt %ENGAGE 8842 and 14.45 wt % MOSTEN TB 003 together with 3.0 wt % SILANRHS 14/032 or SILFIN 29 to form a silane-grafted polyolefin elastomer.The Example 10 silane-grafted polyolefin elastomer was then extrudedwith 2.0 wt % MBF-AC170EVA microencapsulated blowing agent, 3 wt %Ambicat LE4472 condensation catalyst, and 0.7 wt % AD-2 process aide toform a foamed silane-crosslinkable polyolefin elastomer, which was thenextruded into the form of an uncured sealing member. The Example 10foamed silane-crosslinkable polyolefin elastomer of the uncured sealingmember was then cured at ambient temperature and humidity to form afoamed (micro-dense) silane-crosslinked polyolefin elastomer, consistentwith the elastomers of the disclosure. The composition of Example 10 isprovided in Table 11 below and the material properties associated withits foamed (micro-dense) silane-crosslinked polyolefin blend areprovided in Table 12 below.

Example 11

Example 11 (Ex. 11) or ED76-4E was produced by extruding 19.00 wt %ENGAGE 8150, 58.00 wt % ENGAGE 8842, and 20.00 wt % MOSTEN TB 003together with 3.0 wt % SILAN RHS 14/032 or SILFIN 29 to form asilane-grafted polyolefin elastomer. The Example 11 silane-graftedpolyolefin elastomer was then extruded with 2.0 wt % MBF-AC170EVAmicroencapsulated blowing agent, 3 wt % Ambicat LE4472 condensationcatalyst, and 0.7 wt % AD-2 process aide to form a foamedsilane-crosslinkable polyolefin elastomer, which was then extruded intoan uncured sealing member. The Example 11 foamed silane-crosslinkablepolyolefin elastomer of the uncured sealing member was then cured atambient temperature and humidity to form a foamed (micro-dense)silane-crosslinked polyolefin elastomer, consistent with the elastomersof the disclosure. The composition of Example 11 is provided in Table 11below and the material properties associated with its foamed(micro-dense) silane-crosslinked polyolefin blend are provided in Table12 below.

Example 12

Example 12 (Ex. 12) or ED76-5 was produced by extruding 19.00 wt %ENGAGE 8150, 53.00 wt % ENGAGE 8842, and 25.00 wt % MOSTEN TB 003together with 3.0 wt % SILAN RHS 14/032 or SILFIN 29 to form thesilane-grafted polyolefin elastomer. The Example 12 silane-graftedpolyolefin elastomer was then extruded with 2.0 wt % MBF-AC170EVAmicroencapsulated blowing agent, 3 wt % Ambicat LE4472 condensationcatalyst, and 0.7 wt % AD-2 process aide to form a foamedsilane-crosslinkable polyolefin elastomer, which was then extruded intoan uncured sealing member. The Example 12 foamed silane-crosslinkablepolyolefin elastomer of the uncured sealing member was then cured atambient temperature and humidity to form a foamed silane-crosslinkedpolyolefin elastomer, consistent with the elastomers of the disclosure.The composition of Example 12 is provided in Table 11 below and thematerial properties associated with its foamed (micro-dense)silane-crosslinked polyolefin blend are provided in Table 12 below.

Example 13

Example 13 (Ex. 13) or ED76-6 was produced by extruding 16.36 wt %ENGAGE 8150, 45.64 wt % ENGAGE 8842, and 35.00 wt % MOSTEN TB 003together with 3.0 wt % SILAN RHS 14/032 or SILFIN 29 to form thesilane-grafted polyolefin elastomer. The Example 4 silane-graftedpolyolefin elastomer was then extruded with 2.0 wt % MBF-AC170EVAmicroencapsulated blowing agent, 3 wt % Ambicat LE4472 condensationcatalyst, and 0.7 wt % AD-2 process aide to form a foamedsilane-crosslinkable polyolefin elastomer, which was then extruded intoan uncured sealing member. The Example 13 foamed silane-crosslinkablepolyolefin elastomer of the uncured sealing member was then cured atambient temperature and humidity to form a foamed (micro-dense)silane-crosslinked polyolefin elastomer, consistent with the elastomersof the disclosure. The composition of Example 13 is provided in Table 11below and the material properties associated with its foamed(micro-dense) silane-crosslinked polyolefin blend are provided in Table12 below.

TABLE 11 Ingredients Ex. 10 Ex. 11 Ex. 12 Ex. 13 ENGAGE 8150 — 19.0019.00 16.36 ENGAGE 8842 82.55 58.00 53.00 45.64 MOSTEN TB 003 14.4520.00 25.00 35.00 SILAN RHS 14/032 or SILFIN 29 3.00 3.00 3.00 3.00TOTAL 100 100 100 100

TABLE 12 Property Test Method Units/Output Ex. 1 Ex. 2 Ex. 3 Ex. 4Physical Density ASTM D297 g/cc 0.67 0.66 0.67 0.69 Properties HardnessASTM D412 Shore A 60 67 69 87 Die C Tensile ASTM D412 MPa 5.0 7.2 8.77.6 Die C Elongation ASTM D412 % 160 174 203 293 Die C Tear C ASTM D624N/mm 12.6 22.8 22.5 46.8 Die C Aged Hardness Heat Age ASTM D573 Change 20 1 1 Properties (70 h/70° C.) (Shore A) Tensile Heat Age ASTM D573 %Change 12.6 5.5 −0.8 7 (70 h/70° C.) Elongation Heat Age ASTM D573 %Change −0.6 −7.2 −13.5 −12.8 (70 h/70° C.) Compression Plied C/S (22h/70° C.) ASTM D395 % 40 41 61 78 Set Method B Miscellaneous WaterAbsorption MS-AK-92 % 0.5 0.2 0.7 0.5 Ozone Resistance ASTM D1149 — NoNo No No (168 h/40% Cracks Cracks Cracks Cracks Elongation) Odor SAEJ1351 No odor wet Pass Pass Pass Pass or dry Paint Staining ASTM D925 —No No No No (24 h/70° C.) Method A Staining Staining Staining Staining

For purposes of this disclosure, the term “coupled” (in all of itsforms, couple, coupling, coupled, etc.) generally means the joining oftwo components directly or indirectly to one another. Such joining maybe stationary in nature or movable in nature. Such joining may beachieved with the two components and any additional intermediate membersbeing integrally formed as a single unitary body with one another orwith the two components. Such joining may be permanent in nature or maybe removable or releasable in nature unless otherwise stated.

It is also important to note that the construction and arrangement ofthe elements of the device as shown in the exemplary embodiments isillustrative only. Although only a few embodiments of the presentinnovations have been described in detail in this disclosure, thoseskilled in the art who review this disclosure will readily appreciatethat many modifications are possible (e.g., variations in sizes,dimensions, structures, shapes and proportions of the various elements,values of parameters, mounting arrangements, use of materials, colors,orientations, etc.) without materially departing from the novelteachings and advantages of the subject matter recited. For example,elements shown as integrally formed may be constructed of multiple partsor elements shown as multiple parts may be integrally formed, theoperation of the interfaces may be reversed or otherwise varied, thelength or width of the structures and/or members or connector or otherelements of the system may be varied, the nature or number of adjustmentpositions provided between the elements may be varied. It should benoted that the elements and/or assemblies of the system may beconstructed from any of a wide variety of materials that providesufficient strength or durability, in any of a wide variety of colors,textures, and combinations. Accordingly, all such modifications areintended to be included within the scope of the present innovations.Other substitutions, modifications, changes, and omissions may be madein the design, operating conditions, and arrangement of the desired andother exemplary embodiments without departing from the spirit of thepresent innovations.

It will be understood that any described processes or steps withindescribed processes may be combined with other disclosed processes orsteps to form structures within the scope of the present device. Theexemplary structures and processes disclosed herein are for illustrativepurposes and are not to be construed as limiting.

The above description is considered that of the illustrated embodimentsonly. Modifications of the device will occur to those skilled in the artand to those who make or use the device. Therefore, it is understoodthat the embodiments shown in the drawings and described above is merelyfor illustrative purposes and not intended to limit the scope of thearticles, processes and compositions, which are defined by the followingclaims as interpreted according to the principles of patent law,including the Doctrine of Equivalents.

Listing of Non-Limiting Embodiments

Embodiment A is a combined sealing member comprising: a compositioncomprising two or more polyolefin elastomers selected from the groupconsisting of a dense, a micro-dense and a dynamic silane-crosslinkedpolyolefin elastomer having a respective density of less than 0.90g/cm³, less than 0.70 g/cm³, and less than 0.60 g/cm³, wherein thecombined sealing member exhibits a compression set of from about 5.0% toabout 35.0%, as measured according to ASTM D 395 (22 hrs @ 70° C.).

The combined sealing member of Embodiment A wherein the densesilane-crosslinked polyolefin elastomer comprises a first polyolefinhaving a density less than 0.86 g/cm³, a second polyolefin having apercent crystallinity less than 40%, a silane crosslinker, a graftinginitiator, and a non-metal condensation catalyst, wherein the microdensesilane-crosslinked polyolefin elastomer comprises a first polyolefinhaving a density less than 0.86 g/cm³, a second polyolefin having apercent crystallinity less than 40%, a silane crosslinker, a graftinginitiator, a condensation catalyst and a microencapsulated foamingagent, and further wherein the dynamic silane-crosslinked polyolefinelastomer comprises a first polyolefin having a density less than 0.86g/cm³, a second polyolefin having a percent crystallinity less than 40%,a silane crosslinker, a grafting initiator, a condensation catalyst anda foaming agent.

The combined sealing member of Embodiment A or Embodiment A with any ofthe intervening features wherein the compression set is from about 15.0%to about 35.0%, as measured according to ASTM D 395 (22 hrs @ 70° C.).

The combined sealing member of Embodiment A or Embodiment A with any ofthe intervening features wherein the density is from about 0.50 g/cm³ toabout 0.89 g/cm³.

The combined sealing member of Embodiment A or Embodiment A with any ofthe intervening features wherein the silane-crosslinked polyolefinelastomer exhibits a crystallinity of from about 5% to about 25%.

The combined sealing member of Embodiment A or Embodiment A with any ofthe intervening features wherein the silane-crosslinked polyolefinelastomer exhibits a glass transition temperature of from about −75° C.to about −25° C.

The combined sealing member of Embodiment A or Embodiment A with any ofthe intervening features wherein the composition is a thermoset, butexhibits thermoplastic properties during processing.

The combined sealing member of Embodiment A or Embodiment A with any ofthe intervening features wherein the sealing member exhibits aweathering color difference of from about 0.25 ΔE to about 2.0 ΔE, asmeasured according to ASTM D2244.

The combined sealing member of Embodiment A or Embodiment A with any ofthe intervening features further comprising: a coloring agent.

Embodiment B is a combined sealing member comprising: a compositioncomprising a first and a second polyolefin elastomer, wherein the firstelastomer comprises a microdense silane-crosslinked polyolefin elastomerhaving a density of less than 0.70 g/cm³, wherein the second elastomercomprises a dense silane-crosslinked polyolefin elastomer having adensity of less than 0.90 g/cm³ or a dynamic silane-crosslinkedpolyolefin elastomer having a density of less than 0.60 g/cm³, andfurther wherein the combined sealing member exhibits a compression setof from about 5.0% to about 35.0%, as measured according to ASTM D 395(22 hrs @ 70° C.).

The combined sealing member of Embodiment B wherein wherein thecompression set is from about 15.0% to about 35.0%, as measuredaccording to ASTM D 395 (22 hrs @ 70° C.).

The combined sealing member of Embodiment B or Embodiment B with any ofthe intervening features wherein the density is from about 0.50 g/cm³ toabout 0.89 g/cm³.

The combined sealing member of Embodiment B or Embodiment B with any ofthe intervening features wherein the silane-crosslinked polyolefinelastomer exhibits a crystallinity of from about 5% to about 25%.

The combined sealing member of Embodiment B or Embodiment B with any ofthe intervening features wherein the silane-crosslinked polyolefinelastomer exhibits a glass transition temperature of from about −75° C.to about −25° C.

Embodiment C is a combined sealing member comprising: a compositioncomprising a first and a second polyolefin elastomer, wherein the firstelastomer comprises a dense silane-crosslinked polyolefin elastomerhaving a density of less than 0.90 g/cm³, wherein the second elastomercomprises a dynamic silane-crosslinked polyolefin elastomer having adensity of less than 0.60 g/cm³, and further wherein the combinedsealing member exhibits a compression set of from about 5.0% to about35.0%, as measured according to ASTM D 395 (22 hrs @ 70° C.).

The combined sealing member of Embodiment C wherein the compression setis from about 15.0% to about 35.0%, as measured according to ASTM D 395(22 hrs @ 70° C.).

The combined sealing member of Embodiment C or Embodiment C with any ofthe intervening features wherein the density is from about 0.50 g/cm³ toabout 0.89 g/cm³.

The combined sealing member of Embodiment C or Embodiment C with any ofthe intervening features wherein the silane-crosslinked polyolefinelastomer exhibits a crystallinity of from about 5% to about 25%.

The combined sealing member of Embodiment C or Embodiment C with any ofthe intervening features wherein the silane-crosslinked polyolefinelastomer exhibits a glass transition temperature of from about −75° C.to about −25° C.

The combined sealing member of Embodiment C or Embodiment C with any ofthe intervening features further comprising: a coloring agent.

What is claimed is:
 1. A combined sealing member comprising: acomposition comprising two or more polyolefin elastomers selected fromthe group consisting of a dense, a micro-dense and a dynamicsilane-crosslinked polyolefin elastomer having a respective density ofless than 0.90 g/cm³, less than 0.70 g/cm³, and less than 0.60 g/cm³,wherein the combined sealing member exhibits a compression set of fromabout 5.0% to about 35.0%, as measured according to ASTM D 395 (22 hrs @70° C.).
 2. The combined sealing member of claim 1, wherein the densesilane-crosslinked polyolefin elastomer comprises a first polyolefinhaving a density less than 0.86 g/cm³, a second polyolefin having apercent crystallinity less than 40%, a silane crosslinker, a graftinginitiator, and a non-metal condensation catalyst, wherein the microdensesilane-crosslinked polyolefin elastomer comprises a first polyolefinhaving a density less than 0.86 g/cm³, a second polyolefin having apercent crystallinity less than 40%, a silane crosslinker, a graftinginitiator, a condensation catalyst and a microencapsulated foamingagent, and further wherein the dynamic silane-crosslinked polyolefinelastomer comprises a first polyolefin having a density less than 0.86g/cm³, a second polyolefin having a percent crystallinity less than 40%,a silane crosslinker, a grafting initiator, a condensation catalyst anda foaming agent.
 3. The combined sealing member of claim 1, wherein thecompression set is from about 15.0% to about 35.0%, as measuredaccording to ASTM D 395 (22 hrs @ 70° C.).
 4. The combined sealingmember of claim 1, wherein the density is from about 0.50 g/cm³ to about0.89 g/cm³.
 5. The combined sealing member of claim 1, wherein thesilane-crosslinked polyolefin elastomer exhibits a crystallinity of fromabout 5% to about 25%.
 6. The combined sealing member of claim 1,wherein the silane-crosslinked polyolefin elastomer exhibits a glasstransition temperature of from about −75° C. to about −25° C.
 7. Thecombined sealing member of claim 1, wherein the composition is athermoset, but exhibits thermoplastic properties during processing. 8.The combined sealing member of claim 1, wherein the sealing memberexhibits a weathering color difference of from about 0.25 ΔE to about2.0 ΔE, as measured according to ASTM D2244.
 9. The combined sealingmember of claim 1, further comprising: a coloring agent.
 10. A combinedsealing member comprising: a composition comprising a first and a secondpolyolefin elastomer, wherein the first elastomer comprises a microdensesilane-crosslinked polyolefin elastomer having a density of less than0.70 g/cm³, wherein the second elastomer comprises a densesilane-crosslinked polyolefin elastomer having a density of less than0.90 g/cm³ or a dynamic silane-crosslinked polyolefin elastomer having adensity of less than 0.60 g/cm³, and further wherein the combinedsealing member exhibits a compression set of from about 5.0% to about35.0%, as measured according to ASTM D 395 (22 hrs @ 70° C.).
 11. Thecombined sealing member of claim 10, wherein the compression set is fromabout 15.0% to about 35.0%, as measured according to ASTM D 395 (22 hrs@ 70° C.).
 12. The combined sealing member of claim 10, wherein thedensity is from about 0.50 g/cm³ to about 0.89 g/cm³.
 13. The combinedsealing member of claim 10, wherein the silane-crosslinked polyolefinelastomer exhibits a crystallinity of from about 5% to about 25%. 14.The combined sealing member of claim 10, wherein the silane-crosslinkedpolyolefin elastomer exhibits a glass transition temperature of fromabout −75° C. to about −25° C.
 15. A combined sealing member comprising:a composition comprising a first and a second polyolefin elastomer,wherein the first elastomer comprises a dense silane-crosslinkedpolyolefin elastomer having a density of less than 0.90 g/cm³, whereinthe second elastomer comprises a dynamic silane-crosslinked polyolefinelastomer having a density of less than 0.60 g/cm³, and further whereinthe combined sealing member exhibits a compression set of from about5.0% to about 35.0%, as measured according to ASTM D 395 (22 hrs @ 70°C.).
 16. The combined sealing member of claim 15, wherein thecompression set is from about 15.0% to about 35.0%, as measuredaccording to ASTM D 395 (22 hrs @ 70° C.).
 17. The combined sealingmember of claim 15, wherein the density is from about 0.50 g/cm³ toabout 0.89 g/cm³.
 18. The combined sealing member of claim 15, whereinthe silane-crosslinked polyolefin elastomer exhibits a crystallinity offrom about 5% to about 25%.
 19. The combined sealing member of claim 15,wherein the silane-crosslinked polyolefin elastomer exhibits a glasstransition temperature of from about −75° C. to about −25° C.
 20. Thecombined sealing member of claim 15, further comprising: a coloringagent.